JP2019116530A - Resin composition, molding and method for producing molding - Google Patents

Abstract

To provide a resin composition that can improve a zeolite fill factor of the resin composition even when using zeolite with an uncontrolled grain size and has excellent mechanical strength.SOLUTION: A resin composition has surface-treated zeolite 30-95 mass% and a resin 5-70 mass%. The surface treatment is at least one of silane coupling agent treatment, isocyanate compound treatment, thiol compound treatment, alcohol compound treatment, and epoxy compound treatment.SELECTED DRAWING: None

Description

The present invention relates to a resin composition comprising a zeolite and a resin, a molded product using the resin composition, and a method for producing the molded product.

Zeolites are used in various applications because they have functions such as adsorption, sustained release, and ion exchange.
A resin composition containing zeolite, for example, a technology for obtaining a cured product having a light weight and excellent mechanical strength by using a resin composition containing a predetermined particle size of zeolite and a thermosetting resin in predetermined amounts. Patent Document 1) and a technique (Patent Document 2) for preventing condensation of a semiconductor component with a resin composition in which zeolite is contained in a curable resin are disclosed.

  However, in the prior art of Patent Documents 1 and 2, etc., the packing ratio of zeolite in the resin composition is increased by adjusting the particle size of zeolite, and a high packing ratio can not be realized with zeolite whose particle size is not adjusted. .

Unexamined-Japanese-Patent No. 10-219121 JP, 2006-70054, A

  The present invention has been made in view of such circumstances, and the present invention solves the above-mentioned problems of the prior art, and even in the case of using zeolite whose particle size is not adjusted, the filling ratio of zeolite in the resin composition It is an object of the present invention to provide a resin composition capable of enhancing the mechanical strength and excellent mechanical strength and a method for producing the same.

  As a result of intensive investigations by the present inventors, it is possible to increase the packing ratio of zeolite in the resin composition and to obtain a resin composition having excellent mechanical strength by using the surface-treated zeolite. Found out. The present invention has been completed based on such findings.

The present invention provides the following [1] to [15].
[1] A resin composition comprising a surface-treated zeolite and a resin.
[2] The resin composition of [1], wherein the surface treatment is at least one of a silane coupling agent treatment, an isocyanate compound treatment, a thiol compound treatment, an acid compound treatment, an alcohol compound treatment, and an epoxy compound treatment.
[3] The resin composition of [2], wherein the silane coupling agent treatment uses a silane coupling agent having one or more selected from amino group, epoxy group, (meth) acryloyl group and triazine thiol group object.
[4] The resin composition of [2], wherein the isocyanate compound treatment uses an isocyanate compound having a (meth) acryloyl group.
[5] The resin composition of [2], wherein the thiol compound treatment uses a primary and / or secondary thiol compound.
[6] The resin composition of any one of [1] to [5], wherein the zeolite is a synthetic zeolite.
[7] The crystal structure of the synthetic zeolite is at least one selected from the group consisting of LTA type, FAU type, BEA type, LTL type, MFI type, MWW type, FER type and MOR type as a structural code, The resin composition of [6].
[8] The crystal structure of the synthetic zeolite is at least one selected from the group consisting of A-type, X-type, β-type, Y-type, L-type, ZSM-5 type, MCM-22 type, ferrierite type and mordenite type The resin composition of [6], which is a species.
[9] The resin composition according to any one of [1] to [8], wherein the resin is a thermosetting resin.
[10] The resin composition of [9], wherein the thermosetting resin is at least one of an epoxy resin, a phenol resin, an unsaturated polyester resin, a vinyl ester resin, a maleimide resin, a urethane resin, and a urea resin.
[11] The resin composition according to any one of [1] to [8], wherein the resin is a thermoplastic resin.
[12] A molded article having adsorptivity, sustained release and ion exchange properties obtained by molding the resin composition of [1] to [11].
[13] A step of mixing and stirring the zeolite and the surface treatment agent to apply surface treatment to the zeolite, a step of mixing the zeolite surface-treated in the above step and a thermosetting resin to obtain a resin composition, and A method for producing a molded product, comprising the step of molding a resin composition to obtain a molded product having adsorptivity, sustained release and ion exchange properties.
[14] A step of dissolving a surface treatment agent in part of at least one of a raw material monomer of a vinyl ester resin and an unsaturated polyester resin, and immersing zeolite in the raw material monomer having the surface treatment agent dissolved therein A step of surface treatment, a step of mixing the rest of the raw material monomers of at least one of the zeolite and the vinyl ester resin and the unsaturated polyester resin which are surface-treated in the step to obtain a resin composition, and the resin composition A method for producing a molded product, comprising the step of molding to obtain a molded product having adsorptivity, sustained release, and ion exchange properties.
[15] A step of simultaneously mixing a zeolite, a surface treatment agent and a thermosetting resin to obtain a resin composition containing the surface-treated zeolite, and molding and processing the resin composition to adsorb and release the resin composition. And a method for producing a molded product, comprising the step of obtaining a molded product having ion exchange properties.

  By using surface-treated zeolite, even when using zeolite whose particle size is not adjusted, the packing ratio of zeolite in the resin composition can be increased, and a resin composition having excellent mechanical strength can be obtained. You can get it.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments.

<Resin composition>
The resin composition of the present invention comprises a surface-treated zeolite and a resin. It contains other components such as antioxidants, plasticizers, lubricants, polymerization initiators, various fillers such as calcium carbonate, titanium oxide, carbon black and talc within a range that does not affect desired physical properties and production processes. It can also be done.
The resin as the raw material of the resin composition may be a thermosetting resin or a thermoplastic resin. Further, in the present specification, the resin as the raw material also includes a monomer.
The resin composition of the present invention preferably contains 30 to 95% by mass of zeolite, more preferably 50 to 90% by mass of zeolite, and still more preferably 60 to 80% by mass of zeolite.
By containing the zeolite in an amount of 30% by mass or more, the original functions of the zeolite such as water absorption, dehumidification, deodorization, organic substance adsorption and ion exchange can be expressed.
The resin composition of the present invention preferably contains 5 to 70% by mass of resin, more preferably 10 to 50% by mass of resin, and still more preferably 20 to 40% by mass of resin.
By containing the resin in an amount of 5% by mass or more, the zeolite can be bound to express the strength of the composition.

<Zeolite>
In general, zeolite is a generic term for crystalline aluminosilicates. The zeolite used in the present invention may be either natural or synthetic, but synthetic zeolite is preferred from the viewpoint of the purity of the substance, stability of quality and the like.

[Crystal structure of zeolite]
Generally, the basic unit of the crystal structure (also referred to as a framework structure) possessed by zeolite is a tetrahedron consisting of four oxygen atoms surrounding a silicon atom or an aluminum atom, and these are connected in a three-dimensional direction to form a crystal. Form a structure.
The crystal structure of the zeolite used in the present invention is not particularly limited, and examples thereof include various crystal structures represented by a structural code consisting of three letters in alphabet defined by International Zeolite Association. Examples of the structural code include, for example, LTA, FER, MWW, MFI, MOR, LTL, FAU, BEA. Further, when a preferred embodiment of the crystal structure to be used in the present invention is indicated by the name of crystal structure, it is preferably A-type, X-type, β-type, Y-type, L-type, ZSM-5 type, MCM-22 type, It is at least one selected from the group consisting of ferrierite type and mordenite type, more preferably at least one selected from the group consisting of A type, X type and Y type, still more preferably X type or Y type is there.
In general, zeolite has a cation in its crystal structure, which compensates for the negative charge in the above crystal structure composed of aluminosilicate to compensate for the lack of positive charge. There is.
The zeolite used in the present invention is not particularly limited, but at least one selected from the group consisting of hydrogen ion, lithium ion, calcium ion, sodium ion, potassium ion, magnesium ion and barium ion as the cation. Is a zeolite containing And, more preferably, a zeolite containing at least one member selected from the group consisting of hydrogen ion, lithium ion, calcium ion, sodium ion and potassium ion as the cation, more preferably hydrogen ion, lithium ion, calcium ion And zeolite containing at least one selected from the group consisting of sodium ions and sodium ions.

The zeolite used in the present invention preferably has an average particle size of 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. By setting the average particle diameter to 20 μm or less, the surface of the composition can be smoothed with good dispersibility. The average particle diameter of the zeolite used in the present invention is preferably 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. By setting the particle size of the zeolite to 0.1 μm or more, aggregation of the zeolite can be avoided. Here, the average particle diameter means the volume average diameter (MV) of the particle diameter calculated by the laser diffraction / scattering method.
It is preferable that the particle size of 90 mass% or more of all the zeolite particles is 44 μm or less. Performance stability in mass production can be improved by setting the particle size of 90% by mass or more of all the zeolite particles to 44 μm or less.

[Surface treatment of zeolite]
The zeolite used in the present invention is a synthetic zeolite surface-treated with a surface treatment agent.
The surface treatment is preferably at least one of a silane coupling agent treatment, an isocyanate compound treatment, a thiol compound treatment, an acid compound treatment, an alcohol compound treatment, and an epoxy compound treatment.
By subjecting the surface of the zeolite to the above-mentioned surface treatment, the thermosetting resin can be highly filled, and a strong chemical bond with the thermosetting resin can be made.
However, when the A-type, X-type and other hydrophilic zeolites are subjected to the expression treatment, there is a risk that the hydrophilicity may be reduced, and surface treatment within the range not inhibiting the water absorption function of the hydrophilic zeolite is preferable.
When the hydrophilic zeolite is subjected to surface treatment, it is preferably treated with a surface treatment agent of 0.1 to 80% by mass of the hydrophilic zeolite, preferably 1 to 50% by mass, more preferably 2 to 10% by mass. More preferable. By setting the content to 0.1% by mass or more, the surface treatment effect can be obtained, and by setting the content to less than 80% by mass, it is possible to avoid the risk that the hydrophilic function such as water absorption of hydrophilic zeolite is impaired.

(Silane coupling agent treatment)
For the silane coupling agent treatment, known silane coupling agents used for surface treatment of glass fibers can be used. The silane coupling agent is preferably one having one or more selected from an amino group, an epoxy group, a (meth) acryloyl group, and a triazine thiol group.
When a low concentration aqueous solution of a silane coupling agent or an organic solvent solution is brought into contact with the zeolite surface, hydroxyl groups etc. present on the surface react with silanol groups generated by hydrolysis of the silane coupling agent, or silanol groups react with each other. The resulting oligomer condenses and is adsorbed on the zeolite surface, and a strong chemical bond is formed in the drying process. Thus, on the zeolite surface having an effective anchoring effect, a functional group capable of forming a chemical bond that enables strong adhesion between the organic material layer such as a coating resin layer or laminated FRP and the zeolite is further introduced.

  As a silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyl Hydrochloride of trimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, dithiol triazine propyltrie Kishishiran, and the like.

(Isocyanate compound treatment)
For the isocyanate compound treatment, known isocyanate compounds can be used. The isocyanate compound is preferably an isocyanate compound having a (meth) acryloyl group.
As isocyanate compounds, polyfunctional isocyanates such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), etc., and isocyanate compounds having a radical reactive group Certain 2-isocyanatoethyl methacrylates (Karen MOI manufactured by Showa Denko KK), 2-isocyanate ethyl acrylates (Kalens AOI manufactured by Showa Denko KK), 1,1- (bisacryloyloxyethyl) ethyl iso Cinanate (Karen BEI manufactured by Showa Denko KK), 2-isocyanate ethyl acrylate (AOI-VM manufactured by Showa Denko KK) and the like can be mentioned.

(Thiol compound treatment)
For the thiol compound treatment, a compound having a thiol group (hereinafter, referred to as a thiol compound), which can be easily obtained as a commercial product, can be used. The thiol compound is preferably a primary and / or secondary thiol compound.
As a commercially available thiol compound, pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Mitsubishi Chemical Corporation, QX40, Toray Fine Chemical Co., Ltd., QE-340M), ether type primary thiol (Cognis (Cognis) ), Cup Cure 3-800,), 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK, Kalen MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karen MT PE1 manufactured by Showa Denko KK) 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H A)-Trion (manufactured by Showa Denko KK, Kalens MT NR1) and the like. Among them, Curence MT PE1 is excellent in stability in epoxy resin.

(Acid compound treatment)
For the acid compound treatment, a compound containing a carboxylic acid, a sulfone group, etc. (hereinafter referred to as an acid compound) can be used. As the carboxylic acid, carboxylic acids such as acetic acid, propionic acid and benzoic acid, and acid compounds such as benzenesulfonic acid and alkylbenzenesulfonic acid can be used.

(Alcohol compound treatment)
For the alcohol compound treatment, a compound containing a hydroxyl group (hereinafter, an alcohol compound) can be used. The alcohol compound is preferably a primary and / or secondary alcohol compound. As commercially available alcohol compounds, in addition to aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol and propylene glycol, phenol compounds such as phenol, resorcinol and catechol can be used.

(Epoxy compound treatment)
For the epoxy compound treatment, monofunctional epoxy compounds such as glycidyl (meth) acrylate, allyl glycidyl ether, phenyl glycidyl ether and the like, and as an alicyclic epoxy compound, Celoxide 2021 P (difunctional alicyclic epoxy) manufactured by Daicel Corporation, And Celoxide 2000 (alicyclic epoxy having a vinyl group). Alternatively, the epoxy resin described in [0025] may be used. A catalyst such as a tertiary amine may be used in combination with the epoxy compound treatment.

A known method can be used to treat the zeolite surface with each surface treatment agent. Each surface treatment agent may be mixed and stirred directly into the zeolite powder, or the zeolite may be diluted to several percent to several tens percent with a solvent, and the zeolite may be at a temperature of about 100 ° C. for 1 minute to several minutes. After being immersed for a day, it may be withdrawn and dried at ambient temperature to about 100 ° C. for 1 minute to several hours. Moreover, surface treatment can also be efficiently performed using an acid / base catalyst as needed.
Specifically, the zeolite and the surface treatment agent may be mixed in a mortar or the like, or mixed in a ball mill, a Henschel mixer or the like, and mixed and stirred. The efficiency of the surface treatment can be increased by heating simultaneously with or after mixing as required. Moreover, when using hydrophilic zeolite, it is preferable to surface-treat the inside of a dry room or under dry gas atmosphere so that the water absorption function of hydrophilic zeolite may not be impaired.

  In the case of a radical polymerization type resin, a silane coupling agent is added to the reactive diluent to be mixed after completion of the reaction when producing the radical polymerization type resin, and the zeolite is contained therein at normal temperature to about 100 ° C for 1 minute to several days The surface treatment may be advanced by immersion, and the resin composition may be manufactured by mixing the remaining radically polymerizable resin components at the end of the reaction.

<Resin>
[Thermosetting resin]
A known thermosetting resin can be used. For example, one or more selected from an epoxy resin, a phenol resin, an unsaturated polyester resin, a vinyl ester resin, a maleimide resin, a urethane resin, and a urea resin can be used, and other resins may be further contained.

(Epoxy resin)
The epoxy resin may be produced by a known method, and a thermosetting epoxy resin having at least two epoxy groups in one component is preferable. As such an epoxy resin, for example, ether type bisphenol type epoxy resin, novolac type epoxy resin, polyphenol type epoxy resin, aliphatic type epoxy resin, ester-based aromatic epoxy resin, cyclic aliphatic epoxy resin, ether / ether Well-known things, such as ester-type epoxy resin, are mentioned, A bisphenol A epoxy is the most preferable. An epoxy resin may be used individually by 1 type, and may use 2 or more types together. General-purpose products such as “Epicoat 1001” and “Epicoat 828” manufactured by Mitsubishi Chemical Corporation can be used.
Also, as the epoxy curing agent, known ones can be used. Amine compounds, acid anhydrides, phenolic resins, cationic and anionic catalysts, and the like can be used.

(Phenol resin)
The phenol resin is obtained by condensation polymerization of an addition reaction product of a phenol and an aldehyde, and is not particularly limited, and those known in the art can be used. Examples of the phenol resin include resol type phenol resin and novolac type phenol resin.
The resol-type phenolic resin is not particularly limited, and those known in the art can be used. Examples of phenols used as raw materials for producing resol type phenol resin include phenol, various cresols, various ethylphenols, various xylenols, various butylphenols, various octylphenols, various nonylphenols, various phenylphenols, various cyclohexylphenols, catechols, resorcinol, Hydroquinone etc. can be used individually or in mixture of 2 or more types. Examples of aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, hexyl aldehyde, benzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, hydroxymethyl benzaldehyde, glyoxal, crotonaldehyde, glutaraldehyde and the like. Formaldehyde and paraformaldehyde are preferred for practical use. The preferred resol-type phenolic resin has a viscosity of 500 to 8000 mPa · s (25 ° C.), a specific gravity of 1.15 to 1.30, a pH of 6.6 to 7.2, and a nonvolatile content of 40 to 80%. It is a liquid resol type phenolic resin. Such resol type phenol resin is commercially available, and for example, "BRL-240" or "BRL-1017" manufactured by Aika SDK Phenol Co., Ltd. can be used.
The novolac type phenolic resin is not particularly limited, and those known in the art can be used. Phenols used as raw materials for producing novolac-type phenolic resin include, for example, phenol, various cresols, various ethylphenols, various xylenols, various butylphenols, various octylphenols, various nonylphenols, various phenylphenols, various cyclohexylphenols, catechols, resorcinol, hydroquinones Etc. These phenols may be used alone or in combination. As aldehydes, formaldehyde, acetaldehyde, paraformaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, hexyl aldehyde, benzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, hydroxymethyl benzaldehyde, glyoxal, crotonaldehyde, glutaraldehyde etc. can be used particularly Formaldehyde aqueous solution (formalin) is preferably used. These aldehydes may be used alone or in combination. In addition, examples of the novolak catalyst include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid. These catalysts may be used alone or in combination. The number average molecular weight of the novolac type phenolic resin is preferably 300 to 1000. Such novolac type phenol resins are commercially available, and, for example, BRG series such as "BRG-556" and "BRG-557" manufactured by Aika SDK Phenol Co., Ltd. can be used.
The phenolic resin may be thermoset alone, but may be cured in combination with the epoxy resin. The mixing ratio of the epoxy resin and the phenol resin is preferably epoxy equivalent / hydroxyl equivalent = 0.6 / 1.4 to 1.4 / 0.6, more preferably epoxy equivalent / hydroxyl equivalent = 0.8 / 1.2 It is -1.2 / 0.8. If the mixing ratio is outside this range, the water resistance and heat resistance of the cured product may be reduced.

In order to impart the flexibility and water resistance of the cured product, all or part of the phenolic resin may be replaced with a phenolic resin having an alkyl group and / or an allyl group. The phenolic resin having an alkyl group and / or an allyl group is not particularly limited, and those known in the art can be used. As a phenol resin which has an alkyl group, it is a phenol resin manufactured using 4-tert-butyl phenol, 4-octyl phenol, etc. as a raw material, for example, "CKM-1634" by Aika SDK phenol company etc. can be used. .
Further, as a phenol resin having an allyl group, an allylated phenol resin obtained by allyl ether conversion of a phenol resin to Claisen rearrangement can be used. For example, those obtained by allyl etherification and Claisen rearrangement of "BRG series" manufactured by Aika SDK Phenol Co., Ltd. are effective.
The use of a phenol resin having an alkyl group and / or an allyl group is useful for improving the flexibility and water resistance and is also effective for preventing scale adhesion. The replacement ratio may be 100% of the phenol resin, but is preferably 10% or more, more preferably 30% or more. If the amount used is less than 10%, the effect of improving the flexibility and water resistance of the cured product is difficult to achieve.

(Unsaturated polyester resin)
An unsaturated polyester resin is a condensation product (unsaturated polyester) obtained by the esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and optionally a saturated polybasic acid) into a polymerizable monomer such as styrene. It is dissolved. Such unsaturated polyester resins are described in, for example, "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988), "Dictionary of Coatings Dictionary" (edited by Colorants Association, published in 1993), and the like.

The polyhydric alcohol is not particularly limited, but ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. Can be mentioned. These can be used alone or in combination of two or more.
Although it does not specifically limit as unsaturated polybasic acid, Fumaric acid, maleic anhydride, maleic acid, itaconic acid, and these acid anhydrides etc. are mentioned. These can be used alone or in combination of two or more.
The saturated polybasic acid is not particularly limited, and examples thereof include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and acid anhydrides thereof. These can be used alone or in combination of two or more.

  Although the weight average molecular weight of unsaturated polyester is not specifically limited, Preferably it is 2000-6000, More preferably, it is 3000-5000. When the weight average molecular weight of the unsaturated polyester is out of the above range, the balance of the amount of styrene in the resin may be lost, and the strength may not be sufficient.

(Vinyl ester resin)
Vinyl ester resins are those in which the vinyl ester is dissolved in a polymerizable monomer such as styrene. Such vinyl ester resins are also referred to as epoxy acrylate resins, and they are used, for example, as “polyester resin handbook” (published by Nikkan Kogyo Shimbun, 1988) or “paint glossary dictionary” (edited by Colorants Association, published in 1993) Have been described.

  The vinyl ester is not particularly limited, and those known in the art can be used. Examples of vinyl esters include resins obtained by reacting an epoxy resin with an unsaturated monobasic acid (for example, acrylic acid or methacrylic acid), a saturated polybasic acid and / or a polybasic acid and a polyhydric alcohol. The resin obtained by making the saturated polyester or unsaturated polyester which has the obtained terminal carboxyl group, and the epoxy compound which has (alpha), (beta)-unsaturated carboxylic acid ester group react is mentioned.

  Examples of epoxy resins include bisphenol A diglycidyl ether and high molecular weight homologues thereof, novolak type polyglycidyl ether and high molecular weight homologues thereof, and aliphatic glycidyl ethers such as 1,6 hexanediol diglycidyl ether and the like. Be More specifically, the reaction product of bisphenol A and epichlorohydrin, the reaction product of hydrogenated bisphenol A and epichlorohydrin, the reaction product of cyclohexanedimethanol and epichlorohydrin, the reaction product of norbornane dialcohol and epichlorohydrin, tetrabromo bisphenol A Of epichlorohydrin and tricyclodecanedimethanol and epichlorohydrin, aryl cyclic diepoxy carbonate, aryl cyclic diepoxy acetal, aryl cyclic diepoxy carboxylate, novolac glycidyl ether, cresol novolac glycidyl Ether etc. are mentioned. Among these, from the viewpoint of toughness, bisphenol A type diglycidyl ether, novolac type polyglycidyl ether, and brominated compounds thereof are preferable. These can be used alone or in combination of two or more. Further, from the viewpoint of imparting flexibility, a saturated dibasic acid such as adipic acid, sebacic acid or dimer acid may be reacted with the epoxy resin.

  Examples of saturated polybasic acids, unsaturated polybasic acids and polyhydric alcohols may be those described in the above-mentioned (unsaturated polyester resin). Moreover, a glycidyl methacrylate etc. are mentioned as an example of the epoxy compound which has the said (alpha), (beta)-unsaturated carboxylic acid ester group.

  The weight average molecular weight of the vinyl ester is not particularly limited, but is preferably 1,000 to 6,000, and more preferably 1,500 to 5,000. If the weight average molecular weight of the vinyl ester is out of the above range, the adhesion strength of the resin coating layer to the surface of the zeolite may not be sufficient.

  Moreover, urethane (meth) acrylate resin and polyester (meth) acrylate resin are mentioned as resin which can be used similarly to unsaturated polyester resin and vinyl ester resin.

The urethane (meth) acrylate resin, for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, further contains a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound It is a radically polymerizable unsaturated group containing oligomer which can be obtained by making it react. The urethane (meth) acrylate resin can also be obtained by reacting a hydroxyl group-containing (meth) acrylic compound with a polyhydroxy compound or a polyhydric alcohol, and then reacting polyisocyanate.
The polyester (meth) acrylate resin that can be used in the present invention may be selected from (1) polyesters of terminal carboxyl groups obtained from at least one of saturated polybasic acids and unsaturated polybasic acids and polyhydric alcohols. (meth) acrylate obtained by reacting an epoxy compound containing a β-unsaturated carboxylic acid ester group, (2) at least one of a saturated polybasic acid and an unsaturated polybasic acid, and a polyhydric alcohol The terminal obtained from the (meth) acrylate obtained by reacting a hydroxyl group-containing acrylate with the polyester of the terminal carboxyl group to be obtained, (3) at least one of a saturated polybasic acid and an unsaturated polybasic acid, and a polyhydric alcohol (Meth) acrylate obtained by reacting (meth) acrylic acid with polyester of hydroxyl group is there.

(Maleimide resin)
It refers to either bismaleimide, a combination of bismaleimide and an allyl compound, or a combination of bismaleimide and a radically polymerizable compound.

  A commercially available thing can be used as bismaleimide. For example, 4,4'-bismaleimidodiphenylmethane, 1,6-bis (maleimido) hexane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 1,4-bis (maleimido) butane, bisphenol A Bis (4-maleimidophenyl ether), 1,2-bis (maleimido) ethane, N, N′-1,4-phenylenedimaleimide, N, N′-1,3-phenylenedimaleimide, 3,3′- Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) ) Benzene, and 1,3-bis (4-maleimide phenoxy) benzene.

Bismaleimide is preferably used in combination with an allyl compound, preferably an allylated phenol compound, a radically polymerizable compound, an amine or the like.
A commercially available thing can be used as an allyl compound. For example, 2,2'-diallyl bisphenol A, trimethylolpropane diallyl ether, pentaerythritol triallyl ether and the like can be mentioned.
The allylated phenol compound is obtained by a known method of allylating the phenol resins in addition to the above 2,2′-diallyl bisphenol A and heating the obtained allyl etherified phenol resin to carry out Claisen rearrangement May be For example, it is preferable to use an allylated phenol resin obtained by allyl etherification and Claisen rearrangement of “BRG series” manufactured by Aika SDK Phenol Co., Ltd.
The mixing ratio (equivalent ratio) of bismaleimide and allyl compound is preferably maleimide group / allyl group = 1.0 / 5.0 to 5.0 / 1.0, more preferably maleimide group / allyl group = 3.0 /1.0 to 1.0 / 3.0. If the mixing ratio is outside this range, the flexibility and water resistance of the cured product may be reduced.
As the radically polymerizable compound, known radically polymerizable resins, oligomers and monomers can be used. Examples include vinyl ester resins, unsaturated polyester resins, allyl resins, urethane (meth) acrylates, (meth) acrylic monomers, styrene monomers, divinyl benzene and the like. The mixing ratio (equivalent ratio) of bismaleimide and the radically polymerizable compound is preferably maleimide group / radically polymerizable unsaturated group = 5.0 / 1.0 to 1.0 / 5.0, more preferably maleimide group / radical The polymerizable unsaturated group is 3.0 / 1.0 to 1.0 / 3.0. If the mixing ratio is outside this range, the flexibility and water resistance of the cured product may be reduced.
As the amine, primary amines or secondary amines having active hydrogen are preferable. In consideration of heat resistance, examples thereof include diaminodiphenylmethane, diaminodiphenyl sulfone and the like, and the mixing ratio (equivalent ratio) of bismaleimide and amine is preferably maleimide group / active hydrogen = 5.0 / 1.0 to 1 More preferably, the maleimide group / active hydrogen is 3.0 / 1.0 to 1.0 / 3.0. If the mixing ratio is outside this range, the flexibility and water resistance of the cured product may be reduced.
In addition, allyl compounds combined with bismaleimide, radically polymerizable compounds, amines and the like may be used alone or in combination.

(Urethane resin)
The resin used in the present invention may be a resin having a urethane bond in which a polyol compound having a plurality of hydroxyl groups and a polyisocyanate compound having a plurality of isocyanate groups are combined.
As a specific example of a polyol compound, polyether polyol, polyester polyol, a phenol resin etc. can be mentioned. Specific examples of the polyether polyol include, for example, low molecular weight polyol (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol etc.), bisphenols, dihydroxybenzene, propylene oxide, dihydroxybenzene (catechol, resorcine, hydroquinone etc.) The polyether polyol obtained by addition-polymerizing alkylene oxides, such as ethylene oxide, a propylene oxide, a butylene oxide, etc. is mentioned as an initiator, etc. is mentioned.
Specific examples of the polyester polyol include ester components of a polyol component and an acidic component. Examples of the polyol used for esterification include ethylene glycol, diethylene glycol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol glycerin, trimethylolpropane, polypropylene glycol and the like, and as the acid component, For example, succinic acid, adipic acid, sebacic acid, dimer acid, terephthalic acid, isophthalic acid, phthalic acid, maleic acid and the like can be mentioned.
When a phenol resin is used, those described in [0026] can be used.
Specific examples of the polyisocyanate compound include 2,4- or 2,6-tolylene diisocyanate (TDI) or a mixture thereof, p-phenylene dicisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) and a polynuclear mixture thereof Some polymeric MDI etc. are mentioned, Among these, polymeric MDI is suitable especially. As a compounding quantity of an isocyanate component, the range of 0.7-1.5 is appropriate at -OH / -NCO equivalent ratio. As the urethanization catalyst, triethylenediamine, tetramethylguanidine, N, N, N ', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, N, N', N ", N" -An amine catalyst such as pentamethyldipropylene-triamine, N-methylmorpholine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine etc .; dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, Although an organic tin-based catalyst such as dibutyltin dimaleate may be mentioned, a combination of an amine-based catalyst and an organic tin-based catalyst is particularly advantageous. In general, the amount of the urethanization catalyst used is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyol component. Further, in the present invention, a polyurea resin in which a polyamine and a polyisocyanate are reacted instead of a polyol can be used similarly to the polyurethane resin.

(Urea resin)
Urea resin is a resin obtained by addition polymerization of urea and formaldehyde, and known resins can be used. The precondensate of the urea resin used in the present invention may be a general method reaction method. For example, 1 to 3 moles of formaldehyde and 1 mole of urea are mixed with each other at pH 7 to 12, and addition reaction is performed at 30 to 100 ° C. to obtain an initial condensation product of urea resin, curing agent (ammonium chloride, hexamethylene What is obtained by adding and drying tetramine etc. can be used.

(Radically polymerizable unsaturated monomer)
As a radically polymerizable unsaturated monomer used for manufacture of radically polymerizable resin, such as said unsaturated polyester resin, vinyl ester resin, urethane (meth) acrylate resin, polyester (meth) acrylate resin, a styrene monomer, Styrene monomers such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene, chlorostyrene, vinyltoluene, divinylbenzene, etc .; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene Dienes such as: ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, lauryl (meth) acrylate, ( Ta) Dodecyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and phenoxyethyl (meth) acrylate And (meth) acrylic esters such as acrylates. In addition, condensates of unsaturated acids such as maleic acid, fumaric acid, itaconic acid and the like with alcohols can also be used. Also, various polyfunctional (meth) acrylates may be used.
Further, depending on the application, only radically polymerizable unsaturated monomers may be used instead of the above-mentioned respective resins.

(Radical polymerization initiator)
A peroxide catalyst can be used as a radical polymerization initiator for curing the unsaturated polyester resin, vinyl ester resin, urethane (meth) acrylate resin, and polyester (meth) acrylate resin. A well-known thing can be used as a peroxide catalyst. For example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 2,5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetylperoxide Oxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, azobisisobutyronite Le, azobis carboxylic amide can be used.
The amount of the radical polymerization initiator used is preferably 0.2 to 10 parts by weight, more preferably 0.2 to 7.0 parts by weight, and 0.4 to 5.0 parts by weight with respect to 100 parts by weight of the resin composition. Is more preferred.
When the amount is 0.2 parts by weight or more, curing proceeds sufficiently, and when the amount is less than 10 parts by weight, the balance of the resin composition is well maintained, defects occur in the physical properties of the resin composition, and defects occur in the curing reaction itself. It can be avoided to occur.

(Hardening accelerator)
When using the resin composition and maleimide resin which consist of a combination of an epoxy resin and a phenol resin, a hardening accelerator can be used.
Examples of curing accelerators used for the combination of epoxy resin and phenol resin include known curing accelerators of amine type and / or phosphorus type. As the amine promoter, tertiary amines and imidazole compounds are used, and as the phosphorus promoter, promoters such as phosphines are used. Specific examples of the amine promoter include triethylamine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-undecylimidazole, 2-hepta Decylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 tritertiarybutylphosphine-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl -2- phenyl imidazole etc. are mentioned.
Further, specific examples of the phosphorus promoter include triphenylphosphine, tritertiary butyl phosphine, triparatolyl phosphine, diphenylcyclohexyl phosphine, tricyclohexyl phosphine, ethyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, tetraphenyl phosphonium tetra- p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, triphenylphosphine oxide and the like can be mentioned.
The amount of the amine-based and / or phosphorus-based curing accelerator used is 0.05 to 10 parts by weight, preferably 0.3 to 3.0 parts by weight, per 100 parts by weight of the resin composition. If the amount is less than 0.05 parts by weight, the effect of promoting the curing is poor. If the amount is more than 10 parts by weight, a cured product having good water resistance may not be obtained.

  When bismaleimide or a combination of bismaleimide and allyl compound is used, curing of bismaleimide is carried out using a bismaleimide / allyl compound, a peroxide catalyst as an accelerator for curing of bismaleimide / radical polymerization compound, and radical The polymerization may be positively used in combination.

[Thermoplastic resin]
A well-known thing can be used for a thermoplastic resin. For example, polyolefin resin such as polyethylene and polypropylene, polyurethane resin, elastomer resin, acrylic resin, polyvinyl alcohol resin, polyester resin, vinyl chloride resin, fluorine resin, vinyl acetate resin, polyethylene terephthalate resin, polyimide and polyetheretherketone (PEEK) And heat resistant super engineering plastics, etc., as well as composites and copolymers of these resins.

<Molded item>
The resin composition of the present invention can be molded to obtain a molded product having adsorptiveness, sustained release, and ion exchange properties. Examples of the method for producing the molded product include the following methods.

After the zeolite and the surface treatment agent are mixed and stirred to give surface treatment to the zeolite, the surface-treated zeolite and the thermosetting resin are mixed to obtain a resin composition, and the resin composition is molded and processed. Method.
A surface treatment agent is dissolved in part of at least one of the raw material monomers of a vinyl ester resin and an unsaturated polyester resin, and then the zeolite is immersed in the resin in which the surface treatment agent is dissolved to carry out surface treatment on the zeolite. A method in which a resin composition is obtained by mixing the remaining portion of the treated zeolite and at least one of the raw material monomers of a vinyl ester resin and an unsaturated polyester resin, and the resin composition is molded and processed.
A method of simultaneously mixing a zeolite, a surface treatment agent and a thermosetting resin to obtain a resin composition containing the surface-treated zeolite, and molding and processing the resin composition.
The forming process can be performed by a method such as heat curing, photo curing, addition of a polymerization initiator and the like to the resin composition and curing. Moreover, when a resin composition is a thermoplastic resin, after mixing the surface-treated zeolite and a thermoplastic resin, it can carry out by methods, such as heat molding.

  The mixing of the surface-treated zeolite and the resin can be carried out by a known method. Although it may mix simply, you may use a blender and a kneader. In the case of using a dry molding material, they are mixed in a blender or the like and crushed using a hammer mill or a crusher.

  Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1
[Surface treatment of zeolite]
Synthetic zeolite (manufactured by Union Showa Co., Ltd., molecular sieve 3A powder): 100 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd., KBM-403): 2.22 g (0.01 mol) After mixing and stirring for 6 hours using a ball mill, surface-treated zeolite-1 was obtained.
[Preparation of a curable resin composition]
Using a blender, 80 g of the surface-treated zeolite-1 and 20 g of a solid resol-type phenol resin (manufactured by Aika SDK Phenol Co., Ltd., BRP 406) were mixed to obtain a curable resin composition-1.
[Molding]
Using a mold having a thickness of 3 mm, the curable resin composition-1 was heated and pressed at 150 ° C. for 3 hours to obtain a molded product-1.
[Performance measurement]
When the water absorption rate of molded product 1 was measured, high water absorption ability was recognized at 15.5 mass%, and as a result of performing bending strength measurement according to JIS K 7171: 2016 (hereinafter referred to as JIS K 7171), 88.1 MPa and good strength there were. The results are shown in Table 1.

Example 2
[Surface treatment of zeolite]
Synthetic zeolite (manufactured by Union Showa Co., Ltd., molecular sieve 3A powder): 100 g N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu silicon Co., Ltd. KBM-603): 2.22 g (0.01 mol) was mixed and stirred for 6 hours using a ball mill to obtain surface-treated zeolite-2.
[Synthesis of Allylated Phenolic Resin]
In a flask equipped with a stirrer and a reflux condenser, potassium carbonate: 720 g, triphenylphosphine: 12 g, water: 1100 g, 5% Pd / C: 4 g, phenol novolac resin (manufactured by Aika SDK Phenol Co., Ltd., BRG 556): A charge of 104 g (1.0 equivalent), allyl acetate: 569 g (1.2 equivalent) was added, and the reaction was continued at 90 ° C. for 8 hours.
Next, the reaction solution was cooled to 40 ° C., 400 g of toluene and 400 g of water were added, and after stirring, the reaction solution was filtered and separated to separate the toluene layer, and toluene and allyl acetate were distilled off under reduced pressure. Thereafter, 400 g of toluene was further added to the residue, this was dissolved in toluene, and the resulting toluene solution was washed with water three times, and then toluene was distilled off under reduced pressure to obtain BRG 556 allyl ether in 95% yield.
The BRG 556 allyl ether was charged in a flask and stirred at 160 ° C. for 3 hours to carry out a Claisen rearrangement reaction to obtain allylated phenol resin-1.
[Preparation of a curable resin composition]
Surface-treated zeolite-2: 80 g and epoxy resin (Mitsubishi Chemical Co., Ltd. make, Epicoat 1001): 8 g, allylated phenol resin-1: 12 g, 2,4,6-tris (dimethylaminomethyl) phenol (DMP- 30): 0.02 g was mixed using a blender to obtain a curable resin composition-2.
[Molding]
The curable resin composition 2 was molded by heating and pressing at 150 ° C. for 3 hours using a mold with a thickness of 3 mm to obtain a molded product-2.
[Performance measurement]
When the water absorption rate of the molded object 2 was measured, high water absorption ability was recognized at 15.6 mass%, and as a result of performing bending strength measurement by JISK7171, it was 97.1 MPa and favorable strength. The results are shown in Table 1.

Example 3
[Surface treatment of zeolite]
Synthetic zeolite (manufactured by Union Showa Co., Ltd., molecular sieve 3A powder): 100 g and 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicon Co., Ltd., KBM-503): 2.48 g (0.01 mol) is mixed The mixture was stirred for 6 hours using a ball mill to obtain surface-treated zeolite-3.
[Preparation of a curable resin composition]
Using a mortar, a vinyl ester resin (Lipoxy R-804, manufactured by Showa Denko K. K.) to which 1% of surface-treated zeolite-3 and peroxide catalyst (Nippon Yushi Co., Ltd., Perbutyl Z.) is added When mixing was attempted and high loading was attempted, the zeolite could be loaded to 70 Wt%. A curable resin composition-3 was obtained.
[Molding]
The curable resin composition 3 was molded by heating and pressing at 120 ° C. for 5 minutes using a mold with a thickness of 3 mm to obtain a molded product-3.
[Performance measurement]
When the water absorption rate of the molding 3 was measured, high water absorption ability was recognized at 13.5 mass%, and as a result of performing bending strength measurement by JISK7171, it was 138.4 MPa and favorable strength. The results are shown in Table 1.

Example 4
[Surface treatment of zeolite]
Synthetic zeolite (manufactured by Union Showa Co., Ltd., molecular sieve 13X powder): 100 g, pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K. K., Karen MT PE-1): 5.44 g ( After immersing in a solution in which 0.01 mol) was dissolved in 500 g of toluene at 30 ° C. for 2 hours, the toluene was removed, washed with toluene, and dried to obtain a surface-treated zeolite-4.
[Preparation of a curable resin composition]
Surface-treated zeolite-4: 80 g, bismaleimide (manufactured by Kei I Chemical Co., Ltd., BMI): 20 g, peroxide catalyst (manufactured by NOF Corporation, Perbutyl Z): 1.0 g, blender It was used and mixed to obtain a curable resin composition-4.
[Molding]
Using a mold having a thickness of 3 mm, the curable resin composition 4 was heat-pressed at 150 ° C. for 5 minutes to obtain a molded product-4.
[Performance measurement]
When the water absorption rate of the molding 4 was measured, high water absorption ability was recognized at 16.5 mass%, and as a result of performing bending strength measurement by JISK7171, it was 92.3 MPa and favorable strength. The results are shown in Table 1.

Example 5
[Surface treatment of zeolite]
Immersed at 50 ° C for 4 minutes in a solution of 2.50 g (0.01 mol) of diphenylmethane diisocyanate (MDI) in 100 g of synthetic zeolite (Molecular sieve 3A powder, manufactured by Union Showa Co., Ltd.) in 500 g of toluene Then, the toluene was removed, and the residue was further washed with toluene and dried to obtain surface-treated zeolite-5.
[Preparation of a curable resin composition]
Surface-treated zeolite-5: 70 g and unsaturated polyester resin (manufactured by Showa Denko KK, Ligorac 1557): 30 g, peroxide catalyst (manufactured by Nippon Oil and Fats Co., Ltd., Perbutyl Z): 1.0 g The resulting mixture was mixed to obtain a curable resin composition-5.
[Molding]
A curable resin composition-5 was molded by heating and pressing at 120 ° C for 3 minutes using a mold having a thickness of 3 mm to obtain a molded product-5.
[Performance measurement]
When the water absorption rate of the molded object 5 was measured, high water absorption ability was recognized at 14.0 mass%, and as a result of performing bending strength measurement by JISK7171, it was 131.7 Pa and favorable strength. The results are shown in Table 1.

Example 6
[Surface treatment of zeolite]
Synthetic zeolite (manufactured by Union Showa Co., Ltd., molecular sieve 3A powder): 100 g, manufactured by Showa Denko Co., Ltd .: PE-1: 5.44 g (0.01 mol), 2-methacryloyloxyethyl isocyanate Denko Co., Ltd. product, Karenz MOI): Immersed in a solution of 2.50 g (0.01 mol) in 500 g of toluene at 40 ° C. for 5 minutes, after removing the toluene, further washing with toluene and drying Surface-treated zeolite-6 was obtained.
[Preparation of a curable resin composition]
Surface-treated zeolite-6: 70 g, acrylic monomer (Shin-Nakamura Chemical Co., Ltd., BPE-500): 30 g, peroxide catalyst (NIPO Yushi Co., Ltd., Perbutyl Z): 1.0 g, It mixed using the blender and obtained curable resin composition-6.
[Molding]
The curable resin composition 6 was heat-pressed at 120 ° C. for 5 minutes using a mold having a thickness of 3 mm to obtain a molded product 6.
[Performance measurement]
When the water absorption rate of the molded object 6 was measured, high water absorption ability was recognized at 14.7 mass%, and as a result of performing bending strength measurement by JISK7171, it was a favorable strength with 128.7 MPa. The results are shown in Table 1.

Example 7
[Surface treatment of zeolite]
In a kneader, 100 g of synthetic zeolite (Molecular Sieve 3A powder, manufactured by Union Showa Co., Ltd.) and 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Silicon Co., Ltd.): 2.48 g (0. The mixture was stirred with 12 g of styrene in which 01 mol) was dissolved and allowed to stand for 24 hours to obtain surface-treated zeolite / styrene-1.
[Synthesis of vinyl ester]
In a flask equipped with a stirrer and a reflux condenser, 186 g of bisphenol A epoxy resin (Epiclon 840, manufactured by DIC Corporation) is charged, and 2,4,6-tris (dimethylaminomethyl) phenol is maintained at 100 ° C. 86 g of methacrylic acid in which 0.8 g of DMP-30 and 0.08 g of hydroquinone were dissolved was added dropwise, and stirring was continued at 120 ° C., and cooling was performed at an acid value of 5 to obtain vinyl ester-1.
[Preparation of a curable resin composition]
Surface-treated zeolite in a kneader / Styrene-1: 114.48 g of vinyl ester-1: 15 g and Perbutyl Z: 0.3 g are mixed and stirred by a kneader to obtain a curable resin composition-7 (77% by mass of zeolite) The
[Molding]
The curable resin composition 7 was molded by heating and pressing at 120 ° C. for 3 minutes using a mold having a thickness of 3 mm to obtain a molded product 7.
[Performance measurement]
When the water absorption rate of the molding 7 was measured, high water absorption ability was recognized at 15.1 mass%, and as a result of performing bending strength measurement by JISK7171, it was 131.3 MPa and favorable strength. The results are shown in Table 1.

Example 8
Simultaneous mixing
100 g, 3-methacryloxypropyl trimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd., KBM-503): 2.48 g (0.01 mol), synthetic zeolite (Molecular Showa Co., Ltd. product, molecular sieve 3A powder) in a kneader A mixture of 16 g of styrene, 24 g of vinyl ester-1 and 0.3 g of perbutyl Z: 0.3 g was stirred and allowed to stand at room temperature for 3 days to obtain a curable resin composition-8.
[Molding]
The curable resin composition 8 was heat-pressed at 120 ° C. for 3 minutes using a mold having a thickness of 3 mm to obtain a molded product-8.
[Performance measurement]
When the water absorption rate of the molded object-8 was measured, high water absorption ability was recognized at 14.2 mass%, and as a result of performing bending strength measurement by JISK7171, it was 135.9 MPa and favorable strength. The results are shown in Table 1.

Example 9
Simultaneous mixing
The reaction was carried out in the same manner as in Example 8 except that the synthetic zeolite was changed to HiSiv 3000 powder manufactured by Union Showa Co., Ltd. to obtain a curable resin composition -9.
[Molding]
A curable resin composition-9 was molded by heating and pressing at 120 ° C for 3 minutes using a mold having a thickness of 3 mm to obtain a molded product-9.
[Performance measurement]
When the toluene adsorption rate of the molded object-9 was measured, high organic substance adsorption capacity was recognized at 4.5 mass%, and as a result of performing bending strength measurement by JISK7171, it was 130.1 MPa and favorable strength. The results are shown in Table 1.

Comparative Example 1 (Comparison with Example 2)
[Preparation of a curable resin composition]
Synthetic zeolite (Molecular Showa Co., Ltd. product, molecular sieve 3A powder): 80 g and epoxy resin as Mitsubishi Chemical Co., Ltd. product Epicoat 1001: 8 g, allylated phenol resin-1: 12 g, 2, 4, 6- Tris (dimethylaminomethyl) phenol (DMP-30): 0.02 g was mixed using a blender to obtain a curable resin composition-2 '.
[Molding]
A curable resin composition-2 'was heated and pressed at 150 ° C for 3 hours using a mold having a thickness of 3 mm to obtain a molded product-2'. To be molded.
[Performance measurement]
When the toluene adsorption rate of the molded product-2 'was measured, a high organic substance adsorption ability was recognized at 5.4 mass%, but as a result of performing bending strength measurement according to JIS K7171, it was as low as 68.9 MPa. The results are shown in Table 1.

Comparative Example 2 (Comparison with Example 3)
[Preparation of a curable resin composition]
Vinyl ester resin (Showa Denko KK), obtained by adding 1% of a peroxide catalyst (Nippon Yushi Co., Ltd., Perbutyl Z) to synthetic zeolite (Molecular sieve 3A powder, manufactured by Union Showa Co., Ltd.) When mixing with Lipox R-804) was attempted using a mortar and high loading was attempted, the zeolite could only be loaded up to 65 Wt%. A curable resin composition-3 'was obtained.
[Molding]
Using a mold having a thickness of 3 mm, the curable resin composition-3 'was heated and pressed at 120 ° C for 5 minutes to obtain a molded article-3'.
[Performance measurement]
As a result of measuring the flexural strength according to JIS K 7171 with a lower value of 12.5% by mass than that of Example 3 when the water absorption rate of the molded product-3 'was measured, it was 93.1MPa as compared with Example 3 and a low strength. Met. The results are shown in Table 1.

Claims (15)

  A resin composition comprising surface-treated zeolite and a resin.   The resin composition according to claim 1, wherein the surface treatment is at least one of a silane coupling agent treatment, an isocyanate compound treatment, a thiol compound treatment, an acid compound treatment, an alcohol compound treatment, and an epoxy compound treatment.   The resin composition according to claim 2, wherein the silane coupling agent treatment uses a silane coupling agent having one or more selected from an amino group, an epoxy group, a (meth) acryloyl group, and a triazine thiol group. .   The resin composition according to claim 2, wherein the isocyanate compound treatment uses an isocyanate compound having a (meth) acryloyl group.   The resin composition according to claim 2, wherein the thiol compound treatment uses a primary and / or secondary thiol compound.   The resin composition according to any one of claims 1 to 5, wherein the zeolite is a synthetic zeolite.   The crystal structure of the synthetic zeolite is at least one selected from the group consisting of LTA type, FAU type, BEA type, LTL type, MFI type, MWW type, FER type and MOR type as a structural code. The resin composition as described in.   The crystal structure of the synthetic zeolite is at least one selected from the group consisting of A-type, X-type, β-type, Y-type, L-type, ZSM-5 type, MCM-22 type, ferrierite type and mordenite type The resin composition according to claim 6.   The resin composition in any one of Claims 1-8 whose said resin is a thermosetting resin.   The resin composition according to claim 9, wherein the thermosetting resin is at least one of an epoxy resin, a phenol resin, an unsaturated polyester resin, a vinyl ester resin, a maleimide resin, a urethane resin, and a urea resin.   The resin composition in any one of Claims 1-8 whose said resin is a thermoplastic resin.   A shaped article having adsorptivity, sustained release, and ion exchange properties obtained by shaping the resin composition according to any one of claims 1 to 11.   The step of mixing and stirring the zeolite and the surface treatment agent to apply surface treatment to the zeolite, and the step of mixing the zeolite surface-treated in the above step and the thermosetting resin and / or the thermoplastic resin to obtain a resin composition And a process for producing a molded product, comprising the steps of: molding the resin composition to obtain a molded product having adsorptivity, sustained release, and ion exchange properties.   Dissolving the surface treatment agent in part of at least one of the raw material monomers of the vinyl ester resin and the unsaturated polyester resin, and immersing the zeolite in the raw material monomer in which the surface treatment agent is dissolved, thereby surface treating the zeolite Applying and forming a resin composition by mixing the remaining portion of the raw material of at least one of the zeolite and the vinyl ester resin and the unsaturated polyester resin which has been surface-treated in the above-mentioned step to obtain a resin composition A method of producing a molded product, comprising the steps of: obtaining a molded product having adsorptiveness, sustained release, and ion exchange properties.   A step of simultaneously mixing the zeolite, the surface treatment agent and the thermosetting resin to obtain a resin composition containing the surface-treated zeolite, and forming the resin composition to process adsorption, sustained release, ion exchange A method for producing a molded article, comprising the step of obtaining a molded article having a property.