JP6955651B2 - Resin composition, molded product and manufacturing method of molded product - Google Patents

Description

The present invention relates to a resin composition composed of 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 adsorptivity, sustained release property, and ion exchange property.
Regarding a resin composition containing zeolite, for example, a technique for obtaining a cured product that is lightweight and has excellent mechanical strength by using a resin composition containing zeolite having a predetermined particle size and a thermosetting resin in a predetermined amount (patented patent). Document 1) and a technique for preventing dew condensation on semiconductor parts by using a resin composition containing zeolite in a curable resin (Patent Document 2) are disclosed.

However, in the prior arts such as Patent Documents 1 and 2, the filling rate of zeolite in the resin composition is increased by adjusting the particle size of zeolite, and a high filling rate cannot be realized with zeolite having an unadjusted particle size. ..

Japanese Unexamined Patent Publication No. 10-219121 Japanese Unexamined Patent Publication No. 2006-70054

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 when zeolite having an unadjusted particle size is used, the filling rate of zeolite in the resin composition It is an object of the present invention to provide a resin composition having excellent mechanical strength and a method for producing the same.

As a result of diligent studies, the present inventors can obtain a resin composition having an excellent mechanical strength while being able to increase the filling rate of zeolite in the resin composition by using the surface-treated zeolite. I found. The present invention has been completed based on such findings.

The present invention provides the following [1] to [15].
[1] A resin composition composed of a surface-treated zeolite and a resin.
[2] The resin composition according to [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 at least one selected from an amino group, an epoxy group, a (meth) acryloyl group, and a triazine thiol group. thing.
[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 according to 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 seed.
[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 product having adsorptivity, sustained release property, and ion exchange property obtained by molding the resin compositions of [1] to [11].
[13] A step of mixing and stirring zeolite and a surface treatment agent to apply a surface treatment to the zeolite, a step of mixing the surface-treated zeolite and a thermosetting resin in the above step to obtain a resin composition, and the above-mentioned steps. A method for producing a molded product, which comprises a step of molding a resin composition to obtain a molded product having adsorptivity, sustained release property, and ion exchange property.
[14] A step of dissolving a surface treatment agent in a part of at least one of the raw material monomers of a vinyl ester resin and an unsaturated polyester resin, and a step of immersing zeolite in the raw material monomer in which the surface treatment agent is dissolved to make a zeolite. A step of subjecting the surface treatment, a step of mixing the balance of at least one of the raw material monomers of the zeolite, the vinyl ester resin, and the unsaturated polyester resin surface-treated in the step to obtain a resin composition, and the step of obtaining the resin composition. A method for producing a molded product, which comprises a step of molding to obtain a molded product having adsorptivity, sustained release property, and ion exchange property.
[15] A step of simultaneously mixing zeolite, a surface treatment agent, and a thermosetting resin to obtain a resin composition containing surface-treated zeolite, and a process of molding the resin composition to have adsorptivity and sustained release. , A method for producing a molded product, which comprises a step of obtaining a molded product having ion exchange property.

By using the surface-treated zeolite, even when a zeolite having an unadjusted particle size is used, the filling rate of the zeolite in the resin composition can be increased, and the resin composition having excellent mechanical strength can be obtained. Obtainable.

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. Contains other components such as antioxidants, plasticizers, lubricants, polymerization initiators, calcium carbonate, titanium oxide, carbon black, talc and other fillers as long as they do not affect the desired physical properties or manufacturing process. You can also do it.
The resin used as the raw material of the resin composition may be a thermosetting resin or a thermoplastic resin. Further, in the present specification, the resin used as a 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 even more preferably 60 to 80% by mass of zeolite.
By containing 30% by mass or more of zeolite, the original functions of zeolite such as water absorption, dehumidification, deodorization, adsorption of organic substances, and ion exchange can be exhibited.
The resin composition of the present invention preferably contains 5 to 70% by mass of the resin, more preferably 10 to 50% by mass of the resin, and further preferably 20 to 40% by mass of the resin.
By containing 5% by mass or more of the resin, the zeolite can be bound and the strength of the composition can be exhibited.

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

[Crystal structure of zeolite]
Generally, the basic unit of the crystal structure (also referred to as skeleton structure) of zeolite is a tetrahedron composed of four oxygen atoms surrounding a silicon atom or an aluminum atom, and these are linked in a three-dimensional direction to form a crystal. Forming 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 structure code consisting of three letters of the alphabet defined by the International Zeolite Association. Examples of structural codes include LTA, FER, MWW, MFI, MOR, LTL, FAU, and BEA codes. Moreover, when a preferable aspect of the crystal structure used in the present invention is shown by the name of the crystal structure, preferably A type, X type, β type, Y type, L type, ZSM-5 type, MCM-22 type, 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, and further preferably X type or Y type. be.
Generally, zeolite has a cation in its crystal structure, and the cation compensates for the negative charge in the 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 the cation is preferably at least one selected from the group consisting of hydrogen ion, lithium ion, calcium ion, sodium ion, potassium ion, magnesium ion and barium ion. It is a zeolite containing. Then, more preferably, the cation contains at least one selected from the group consisting of hydrogen ion, lithium ion, calcium ion, sodium ion and potassium ion, and more preferably hydrogen ion, lithium ion and calcium ion. And a zeolite containing at least one selected from the group consisting of 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 size to 20 μm or less, the dispersibility can be improved and the surface of the composition can be smoothed. The average particle size 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 size means the volume average diameter (MV) of the particle size calculated by the laser diffraction / scattering method.
The particle size of 90% by mass or more of the total zeolite particles is preferably 44 μm or less. Performance stability during mass production can be improved by setting the particle size of 90% by mass or more of the total zeolite particles to 44 μm or less.

[Zeolite surface treatment]
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 applying the above surface treatment to the zeolite surface, it is possible to highly fill the thermosetting resin and to form a strong chemical bond with the thermosetting resin.
However, when the expression treatment is applied to hydrophilic zeolites of type A, X and the like, the hydrophilicity may decrease, and surface treatment within a range that does not impair the water absorption function of the hydrophilic zeolite is preferable.
When surface-treating the hydrophilic zeolite, it is preferable to treat it with a surface treatment agent of 0.1 to 80% by mass of the hydrophilic zeolite, more preferably 1 to 50% by mass, and 2 to 10% by mass. More preferred. When the content is 0.1% by mass or more, the surface treatment effect can be obtained, and when the content is less than 80% by mass, the risk of impairing the hydrophilic function such as water absorption of the hydrophilic zeolite can be avoided.

(Silane coupling agent treatment)
For the silane coupling agent treatment, a known silane coupling agent used for surface treatment of glass fibers or the like can be used. The silane coupling agent preferably has 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, the hydroxyl groups and the like existing on the surface react with the silanol groups generated by the hydrolysis of the silane coupling agent, or the silanol groups are reacted with each other. The oligomer produced by the condensation of silane is adsorbed on the surface of the zeolite, and a strong chemical bond is formed by the drying treatment. In this way, a functional group capable of forming a chemical bond that enables strong adhesion between the zeolite and the organic material layer such as a coating resin layer or laminated FRP is further introduced on the surface of the zeolite having an effective anchoring effect.

As a silane coupling agent, vinyl trimethoxysilane, vinyl triethoxysilane, 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-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silica, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane hydrochloride Examples thereof include salts, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyandiapropyltriethoxysilane, and dithioltriazinepropyltriethoxysilane.

(Isocyanate compound treatment)
A known isocyanate compound can be used for the isocyanate compound treatment. The isocyanate compound is preferably an isocyanate compound having a (meth) acryloyl group.
Examples of the isocyanate compound include diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), which are polyfunctional isocyanates, and isocyanate compounds having a radical reactive group. There are 2-isocyanate ethyl methacrylate (manufactured by Showa Denko Co., Ltd., Karenz MOI), 2-isocyanate ethyl acrylate (manufactured by Showa Denko Co., Ltd., Karenz AOI), 1,1- (bisacryloyloxyethyl) ethyl iso Examples thereof include synate (manufactured by Showa Denko Co., Ltd., Karenz BEI) and 2-isocyanate ethyl acrylate (manufactured by Showa Denko Co., Ltd., AOI-VM).

(Thiol compound treatment)
For the thiol compound treatment, a compound containing a thiol group (hereinafter, thiol compound), which is easily available as a commercially available product, can be used. The thiol compound is preferably a primary and / or secondary thiol compound.
Commercially available thiol compounds include pentaerythritol tetrakis (3-mercaptopropionate) (Mitsubishi Chemical Co., Ltd., QX40, Toray Fine Chemicals Co., Ltd., QE-340M), ether-based primary thiol (Cognis). ), Cup Cure 3-800,), 1,4-bis (3-mercaptobutyryloxy) butane (Showa Denko, Inc., Karenz MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Showa Denko KK, Karenz MT PE1), 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trion (manufactured by Showa Denko KK, Karenz MT NR1) and the like. Among them, Calends MT PE1 is excellent in stability in epoxy resin.

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

(Alcohol compound treatment)
A compound containing a hydroxyl group (hereinafter referred to as an alcohol compound) can be used for the treatment with an alcohol compound. 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, phenolic compounds such as phenol, resorcinol and catechol can be used.

(Epoxy compound treatment)
For epoxy compound treatment, monofunctional epoxy compounds such as glycidyl (meth) acrylate, allyl glycidyl ether, and phenylglycidyl ether, and celloxide 2021P (bifunctional alicyclic epoxy) manufactured by Daicel Co., Ltd. as an alicyclic epoxy compound, Examples thereof include 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.

As a method for treating the zeolite surface using each surface treatment agent, a known method can be used. Each surface treatment agent may be directly mixed in the zeolite powder and stirred, or the zeolite may be mixed in a solution obtained by diluting each surface treatment agent with a solvent to several% to several tens of% at room temperature to about 100 ° C. for 1 minute to several times. After soaking for a day, it may be withdrawn and dried at room temperature to about 100 ° C. for 1 minute to several hours. Further, if necessary, the surface treatment can be efficiently performed using an acid / base catalyst.
Specifically, the zeolite and the surface treatment agent can be put in a mortar or the like and mixed, or put in a ball mill, a Henschel mixer or the like and mixed and stirred. The efficiency of surface treatment can be improved by heating at the same time as or after mixing as needed. When hydrophilic zeolite is used, it is preferable to perform surface treatment in a dry room or in a dry gas atmosphere so as not to impair the water absorption function of the hydrophilic zeolite.

In the case of a radical polymerization type resin, a silane coupling agent is added to a reactive diluent to be mixed after the reaction is completed during the production of the radical polymerization type resin, and zeolite is added therein at room temperature to about 100 ° C. for 1 minute to several days. The resin composition may be produced by immersing and advancing the surface treatment and mixing the remaining radical polymerization type resin component at the end of the reaction.

<Resin>
[Thermosetting resin]
A known thermosetting resin can be used. For example, one or more selected from epoxy resin, phenol resin, unsaturated polyester resin, vinyl ester resin, maleimide resin, urethane resin, and urea resin can be used, and other resins may be 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. Examples of such epoxy resins include ether-type bisphenol-type epoxy resins, novolac-type epoxy resins, polyphenol-type epoxy resins, aliphatic-type epoxy resins, ester-based aromatic epoxy resins, cyclic aliphatic epoxy resins, and ethers. Known ones such as ester type epoxy resins are mentioned, and bisphenol A type epoxy is most preferable. One type of epoxy resin may be used alone, or two or more types may be used in combination. General-purpose products such as "Epicoat 1001" and "Epicoat 828" manufactured by Mitsubishi Chemical Corporation can be used.
Further, as the epoxy curing agent, known ones can be used. Amine compounds, acid anhydrides, phenolic resins, cationic and anionic catalysts, etc. can be used.

(Phenol resin)
The phenol resin is a condensation polymerization product of an addition reaction product of phenols and aldehydes, and is not particularly limited, and those known in the art can be used. Examples of the phenol resin include a resol type phenol resin and a novolak type phenol resin.
The resol type phenol 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 phenolic resins include phenol, various cresols, various ethylphenols, various xylenols, various butylphenols, various octylphenols, various nonylphenols, various phenylphenols, various cyclohexylphenols, catechols, and resosinol. Hydroquinone and the like can be used alone or in combination of two or more. Examples of aldehydes include formaldehyde, acetaldehyde, paraformaldehyde, propylaldehyde, butylaldehyde, barrel aldehyde, hexyl aldehyde, benzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, hydroxymethylbenzaldehyde, glioxal, crotonaldehyde, glutaaldehyde and the like. Formaldehyde and paraformaldehyde are preferable from the viewpoint of practicality. The preferred resole-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 non-volatile content of 40 to 80%. It is a liquid resol type phenol resin. Such a resol type phenol resin is commercially available, and for example, "BRL-240" and "BRL-1017" manufactured by Aica SDK Phenol can be used.
The novolak type phenol resin is not particularly limited, and those known in the art can be used. Phenols used as raw materials for producing novolak-type phenolic resins include, for example, phenol, various cresols, various ethylphenols, various xylenols, various butylphenols, various octylphenols, various nonylphenols, various phenylphenols, various cyclohexylphenols, catechols, resosinol, and hydroquinone. And so on. These phenols may be used alone or in combination. As aldehydes, formaldehyde, acetaldehyde, paraformaldehyde, propylaldehyde, butylaldehyde, barrel aldehyde, hexyl aldehyde, benzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, hydroxymethylbenzaldehyde, glioxal, crotonaldehyde, glutaaldehyde and the like can be used, and in particular. An aqueous formaldehyde solution (formalin) is preferably used. These aldehydes may be used alone or in combination. Examples of the novolacizing 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 novolak type phenol resin is preferably 300 to 1000. Such a novolak type phenol resin is commercially available, and for example, BRG series such as "BRG-556" and "BRG-557" manufactured by Aica SDK Phenol can be used.
The phenol resin may be thermoset alone, or may be cured in combination with an 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, and more preferably epoxy equivalent / hydroxyl equivalent = 0.8 / 1.2. ~ 1.2 / 0.8. If the mixing ratio is out of this range, the water resistance and heat resistance of the cured product may decrease.

For the purpose of imparting flexibility and water resistance of the cured product, all or part of the phenol resin may be replaced with a phenol resin having an alkyl group and / or an allyl group. The phenol resin having an alkyl group and / or an allyl group is not particularly limited, and those known in the art can be used. The phenol resin having an alkyl group is a phenol resin produced by using 4-tertiary butylphenol, 4-octylphenol or the like as a raw material, and for example, "CKM-1634" manufactured by Aica SDK Phenol Co., Ltd. can be used. ..
As the phenol resin having an allylic group, an allylated phenol resin obtained by converting the phenol resin into an allyl ether and rearranging the Claisen rearrangement can be used. For example, the one obtained by converting the "BRG series" manufactured by Aica SDK Phenol into allyl ether and rearranging it with Claisen is effective.
The use of a phenolic resin having an alkyl group and / or an allyl group is useful for improving flexibility and water resistance, and is also effective in 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 obtain.

(Unsaturated polyester resin)
An unsaturated polyester resin transforms a condensation product (unsaturated polyester) from an esterification reaction of a polyhydric alcohol with an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) into a polymerizable monomer such as styrene. It is dissolved. Such unsaturated polyester resins are described in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988) or "Paint Glossary" (edited by Japan Society of Color Material, published in 1993).

The polyhydric alcohol is not particularly limited, but is limited to ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, and 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.
The unsaturated polybasic acid is not particularly limited, and examples thereof include fumaric acid, maleic anhydride, maleic acid, itaconic acid, and acid anhydrides thereof. 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, sebatic acid, and acid anhydrides thereof. These can be used alone or in combination of two or more.

The weight average molecular weight of the unsaturated polyester is not particularly limited, but is preferably 2000 to 6000, and more preferably 3000 to 5000. If the weight average molecular weight of the unsaturated polyester deviates from 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 resin is obtained by dissolving vinyl ester in a polymerizable monomer such as styrene. Such vinyl ester resins are also called epoxy acrylate resins, and are found in "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988) or "Paint Glossary" (edited by Japan Society of Color Material, published in 1993). Have been described.

The vinyl ester is not particularly limited, and a known method can be used. Examples of vinyl esters include resins obtained by reacting an epoxy resin with an unsaturated monobasic acid (eg, acrylic acid or methacrylic acid), saturated polybasic acids and / or unsaturated polybasic acids and polyvalent alcohols. Examples thereof include a resin obtained by reacting a saturated polyester having a terminal carboxyl group or an unsaturated polyester obtained with an epoxy compound having an α, β-unsaturated carboxylic acid ester group.

Examples of epoxy resins include bisphenol A type diglycidyl ether and its high molecular weight homologue, novolak type polyglycidyl ether and its high molecular weight homologue, and aliphatic glycidyl ether such as 1,6-hexanediol diglycidyl ether. Be done. More specifically, a reaction product of bisphenol A and epichlorohydrin, a reaction product of hydride bisphenol A and epichlorohydrin, a reaction product of cyclohexanedimethanol and epichlorohydrin, a reaction product of norbornandi alcohol and epichlorohydrin, tetrabrom bisphenol A. And epichlorohydrin reaction, tricyclodecanedimethanol and epichlorohydrin reaction, alicyclic diepoxy carbonate, alicyclic diepoxy acetal, alicyclic diepoxycarboxylate, novolac glycidyl ether, cresol novolac glycidyl Examples include ether. Among these, bisphenol A type diglycidyl ether, novolac type polyglycidyl ether, and bromines thereof are preferable from the viewpoint of toughness. 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 acid, unsaturated polybasic acid and polyhydric alcohol may be those described in the above description of (unsaturated polyester resin). Further, examples of the epoxy compound having an α, β-unsaturated carboxylic acid ester group include glycidyl methacrylate and the like.

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 adhesive strength of the resin coating layer to the surface of the zeolite may not be sufficient.

Examples of resins that can be used in the same manner as unsaturated polyester resins and vinyl ester resins include urethane (meth) acrylic rate resins and polyester (meth) acrylate resins.

The urethane (meth) acrylate resin is prepared by reacting, for example, a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, and then further adding 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 that can be obtained by reacting. 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 further reacting with a polyisocyanate.
The polyester (meth) acrylate resin that can be used in the present invention includes (1) a polyester having a terminal carboxyl group obtained from at least one of a saturated polybasic acid and an unsaturated polybasic acid, and a polyhydric alcohol. Obtained from (meth) acrylate obtained by reacting an epoxy compound containing a β-unsaturated carboxylic acid ester group, (2) at least one of saturated polybasic acid and unsaturated polybasic acid, and polyvalent alcohol. Terminal obtained from (meth) acrylate obtained by reacting a hydroxyl group-containing acrylate with a polyester having a terminal carboxyl group, (3) at least one of saturated polybasic acid and unsaturated polybasic acid, and a polyhydric alcohol. It is a (meth) acrylate obtained by reacting a hydroxyl group polyester with a (meth) acrylic acid.

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

Commercially available bismaleimide can be used. For example, 4,4'-bismaleimidediphenylmethane, 1,6-bis (maleimide) hexane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, 1,4-bis (maleimide) butane, bisphenol A. Bis (4-maleimide phenyl ether), 1,2-bis (maleimide) ethane, N, N'-1,4-phenylenedi maleimide, N, N'-1,3-phenylenedi maleimide, 3,3'- Didimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4 , 4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene and the like.

Bismaleimide is preferably used in combination with an allylic compound, preferably an allylated phenol compound, a radically polymerizable compound, an amine or the like.
Commercially available allyl compounds can be used. For example, 2,2'-diallyl bisphenol A, trimethylolpropane diallyl ether, pentaerythritol triallyl ether and the like can be mentioned.
The allylated phenol compound was obtained by a well-known method in which, in addition to the above 2,2'-diallyl bisphenol A, phenol resins were allyl etherified and the obtained allyl etherified phenol resin was heated to rearrange the Claisen rearrangement. You may. For example, an allylated phenol resin obtained by converting "BRG series" manufactured by Aica SDK Phenol Co., Ltd. into allyl ether and rearranging Claisen rearrangement can be preferably used.
The mixing ratio (equivalent ratio) of the bismaleimide and the allyl compound is preferably maleimide group / allyl group = 1.0 / 5.0 to 5.0 / 1.0, and more preferably maleimide group / allyl group = 3.0. /1.0 to 1.0 / 3.0. If the mixing ratio is out of this range, the flexibility and water resistance of the cured product may decrease.
As the radically polymerizable compound, known radically polymerizable resins, oligomers and monomers can be used. Examples thereof include vinyl ester resin, unsaturated polyester resin, allyl resin, urethane (meth) acrylate, (meth) acrylic monomer, styrene monomer, divinylbenzene 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 = 3.0 / 1.0 to 1.0 / 3.0. If the mixing ratio is out of this range, the flexibility and water resistance of the cured product may decrease.
As the amine, a primary amine having active hydrogen or a secondary amine is preferable. Considering heat resistance, examples thereof include diaminodiphenylmethane and diaminodiphenylsulfone, and the mixing ratio (equivalent ratio) of bismaleimide and amine is preferably maleimide group / active hydrogen = 5.0 / 1.0 to 1. More preferably than 0.0 / 5.0, maleimide group / active hydrogen = 3.0 / 1.0 to 1.0 / 3.0. If the mixing ratio is out of this range, the flexibility and water resistance of the cured product may decrease.
Further, the allyl compound, the radically polymerizable compound, the amine and the like to be combined with bismaleimide may be used alone or at the same time.

(Urethane resin)
As the resin used in the present invention, a known resin having a urethane bond, which is a combination of a polyol compound having a plurality of hydroxyl groups and a polyisocyanate compound having a plurality of isocyanate groups, can be used.
Specific examples of the polyol compound include polyether polyols, polyester polyols, phenol resins and the like. Specific examples of the polyether polyol include low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols, dihydroxybenzene, propylene oxide, dihydroxybenzene (catechol, resorcin, hydroquinone, etc.). Examples thereof include polyether polyols obtained by addition-polymerizing alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide as an initiator.
Specific examples of the polyester polyol include esterified products 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 examples of the acid component include ethyl glycol, diethylene glycol, 1,3-butanediol, neopentyl glycol, and the like. Examples thereof include succinic acid, adipic acid, sebacic acid, dimer acid, terephthalic acid, isophthalic acid, phthalic acid, maleic acid and the like.
When a phenol resin is used, the one 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 diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) or a polynuclear mixture thereof. A certain polypeptide MDI and the like can be mentioned, and among these, the polypeptide MDI is particularly suitable. The appropriate amount of the isocyanate component to be blended is in the range of 0.7 to 1.5 in terms of the −OH / −NCO equivalent ratio. As the urethanization catalyst, triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, N, N', N', N' -Amine-based catalysts such as pentamethyldipropylene-triamine, N-methylmorpholin, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine; dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, Examples thereof include organotin-based catalysts such as dibutyltin dimalate, but the combined use of an amine-based catalyst and an organotin-based catalyst is particularly advantageous. Generally, the amount of these urethanization catalysts 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 obtained by reacting a polyamine with a polyisocyanate instead of a polyol can be used in the same manner as a polyurethane resin.

(Urea resin)
The urea resin is a resin obtained by addition polymerization of urea and formaldehyde, and known ones can be used. The initial condensate of the urea resin used in the present invention may be a general method reaction method. For example, urea and formaldehyde are mixed with 1 mol of urea at pH 7 to 12, and 1 to 3 mol of formaldehyde is mixed and subjected to an addition reaction at 30 to 100 ° C. to obtain a urea resin initial condensate, and a curing agent (ammonium chloride, hexamethylene chloride) is obtained. Those obtained by adding (tetramine, etc.) and drying can be used.

(Radical polymerizable unsaturated monomer)
Examples of the radically polymerizable unsaturated monomer used for producing a radically polymerizable resin such as the unsaturated polyester resin, vinyl ester resin, urethane (meth) acrylate resin, and polyester (meth) acrylate resin include styrene monomer. Styrene-based monomers such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene, chlorostyrene, vinyltoluene, divinylbenzene; 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, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, di Examples thereof include (meth) acrylic acid esters such as cyclopentenyloxyethyl (meth) acrylate and phenoxyethyl (meth) acrylate. Further, a condensate of an unsaturated acid such as maleic acid, fumaric acid or itaconic acid and an alcohol can also be used. Moreover, you may use various (meth) acrylates of polyfunctionality.
Further, depending on the application, only a radically polymerizable unsaturated monomer may be used instead of each of the above resins.

(Radical polymerization initiator)
A peroxide catalyst can be used as a radical polymerization initiator for curing an unsaturated polyester resin, a vinyl ester resin, a urethane (meth) acrylate resin, or a polyester (meth) acrylate resin. A known peroxide catalyst can be used. 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) hexin-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumylhydroperoxide, acetylper Oxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, azobisisobutyronitrile, azo Biscarboxylic amide or the like 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 preferable.
When it is 0.2 parts by weight or more, curing proceeds sufficiently, and when it is less than 10 parts by weight, the balance of the resin composition is kept good, and the physical properties of the resin composition are defective or the curing reaction itself is defective. It can be avoided to occur.

(Curing accelerator)
When a resin composition composed of a combination of an epoxy resin and a phenol resin or a maleimide resin is used, a curing accelerator can be used.
Examples of the curing accelerator used in the combination of the epoxy resin and the phenol resin include known amine-based and / or phosphorus-based curing accelerators. As the amine-based accelerator, a tertiary amine or imidazole-based compound is used, and as the phosphorus-based accelerator, a phosphine-based accelerator or the like is used. Specific examples of amine-based accelerators include triethylamine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-undecylimidazole, and 2-hepta. Decylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 tritersial butylphosphine-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl -2-phenylimidazole and the like can be mentioned.
Specific examples of phosphorus-based accelerators include triphenylphosphine, tritershally butylphosphine, tripalathylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and tetraphenylphosphonium tetra-. Examples thereof include p-tolylbolate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, triphenylphosphine oxide and the like.
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, based on 100 parts by weight of the resin composition. If it is less than 0.05 parts by weight, the effect of promoting curing is poor, and if it exceeds 10 parts by weight, a cured product having good water resistance may not be obtained.

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

[Thermoplastic resin]
As the thermoplastic resin, known ones can be used. For example, polyolefin resins such as polyethylene and polypropylene, polyurethane resins, elastomer resins, acrylic resins, polyvinyl alcohol resins, polyester resins, vinyl chloride resins, fluororesins, vinyl acetate resins, polyethylene terephthalate resins, polyimides and polyether ether ketones (PEEK). Examples thereof include heat-resistant super-engineering plastics such as, and composites and copolymers of these resins.

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

Zeolite and a surface treatment agent are mixed and stirred to perform surface treatment on the zeolite, and then the surface-treated zeolite and a thermosetting resin are mixed to obtain a resin composition, and the resin composition is molded. Method.
After dissolving the surface treatment agent in a part of at least one of the raw material monomers of the vinyl ester resin and the unsaturated polyester resin, the zeolite is immersed in the resin in which the surface treatment agent is dissolved to perform the surface treatment on the zeolite, and then the surface is treated. A method in which a resin composition is obtained by mixing the treated zeolite with the rest of at least one of a raw material monomer of a vinyl ester resin and an unsaturated polyester resin, and the resin composition is molded.
A method in which zeolite, a surface treatment agent, and a thermosetting resin are mixed at the same time to obtain a resin composition containing surface-treated zeolite, and the resin composition is molded.
The molding process can be carried out by a method such as heat curing, photocuring, addition of a polymerization initiator and the like to the resin composition and curing. When the resin composition is a thermoplastic resin, the surface-treated zeolite and the thermoplastic resin can be mixed and then heat-molded.

The surface-treated zeolite and the resin can be mixed by a known method. It may be simply mixed, but a blender or kneader may be used. When using a dry molding material, mix with a blender or the like and crush using a hammer mill or crusher.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Example 1>
[Zeolite surface treatment]
Synthetic zeolite (Molecular sieve 3A powder manufactured by Union Showa Co., Ltd.): 100 g, 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicon Co., Ltd., KBM-403): 2.22 g (0.01 mol) The mixture was mixed and stirred using a ball mill for 6 hours to obtain surface-treated zeolite-1.
[Preparation of curable resin composition]
Surface-treated zeolite-1: 80 g and solid resole-type phenol resin (Aica SDK Phenol Co., Ltd., BRP406): 20 g were mixed using a blender to obtain a curable resin composition-1.
[Molding]
The curable resin composition-1 was heat-press molded at 150 ° C. for 3 hours using a mold having a thickness of 3 mm to obtain a molded product-1.
[Performance measurement]
When the water absorption rate of the molded product-1 was measured, a high water absorption capacity was observed at 15.5% by mass, and as a result of measuring the bending strength by JISK7171: 2016 (hereinafter referred to as JISK7171), the strength was as good as 88.1 MPa. there were. The results are shown in Table 1.

<Example 2>
[Zeolite surface treatment]
Synthetic zeolite (Molecular sieve 3A powder manufactured by Union Showa Co., Ltd.): 100 g, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (manufactured by Shinetsu Silicon Co., Ltd., KBM-603): 2.22 g (0.01 mol) was mixed and stirred using a ball mill for 6 hours to obtain surface-treated zeolite-2.
[Synthesis of allylated phenol resin]
In a flask equipped with a stirrer and a reflux tube, potassium carbonate: 720 g, triphenylphosphine: 12 g, water: 1100 g, 5% Pd / C: 4 g, phenol novolac resin (manufactured by Aica SDK Phenol Co., Ltd., BRG556): 104 g (1.0 equivalent) and allyl acetate: 569 g (1.2 equivalent) were charged, 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, separated to remove the toluene layer, and toluene and allyl acetate were distilled off under reduced pressure. After that, 400 g of toluene was further added to the residue to dissolve it in toluene, and the resulting toluene solution was washed with water three times, and then toluene was distilled off under reduced pressure to obtain BRG556 allyl ether in a yield of 95%.
This BRG556 allyl ether was placed in a flask and stirred at 160 ° C. for 3 hours to carry out a Claisen rearrangement reaction to obtain an allylated phenol resin-1.
[Preparation of curable resin composition]
Surface-treated zeolite-2: 80 g and epoxy resin (Made by Mitsubishi Chemical Corporation, 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 heat-press molded at 150 ° C. for 3 hours using a mold having a thickness of 3 mm to obtain a molded product-2.
[Performance measurement]
When the water absorption rate of the molded product-2 was measured, a high water absorption capacity was observed at 15.6% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 97.1 MPa. The results are shown in Table 1.

<Example 3>
[Zeolite surface treatment]
Synthetic zeolite (Molecular sieve 3A powder manufactured by Union Showa Co., Ltd.): 100 g mixed with 3-methacryloxypropyltrimethoxysilane (manufactured by Shinetsu Silicon Co., Ltd., KBM-503): 2.48 g (0.01 mol) Then, the mixture was stirred for 6 hours using a ball mill to obtain surface-treated zeolite-3.
[Preparation of curable resin composition]
Vinyl ester resin (Showa Denko KK, Lipoxy R-804) with surface-treated zeolite-3 and peroxide catalyst (Perbutyl Z, manufactured by Nippon Oil & Fats Co., Ltd.) added in a dairy pot. When the mixture was mixed and high filling was attempted, zeolite could be filled up to 70 Wt%. A curable resin composition-3 was obtained.
[Molding]
The curable resin composition-3 was heat-press molded at 120 ° C. for 5 minutes using a mold having a thickness of 3 mm to obtain a molded product-3.
[Performance measurement]
When the water absorption rate of the molded product-3 was measured, a high water absorption capacity was observed at 13.5% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 138.4 MPa. The results are shown in Table 1.

<Example 4>
[Zeolite surface treatment]
Synthetic Zeolite (Union Showa Co., Ltd., Molecular Sieve 13X Powder): 100 g, Pentaerythritol Tetrakis (3-Mercaptobutyrate) (Showa Denko Co., Ltd., Karenz MT PE-1): 5.44 g ( 0.01 mol) was immersed in a solution of 500 g of toluene at 30 ° C. for 2 hours, the toluene was removed, the mixture was further washed with toluene, and dried to obtain surface-treated zeolite-4.
[Preparation of curable resin composition]
Surface-treated zeolite-4: 80 g and bismaleimide (KAI Kasei Co., Ltd., BMI): 20 g, peroxide catalyst (NOF Corporation, Perbutyl Z): 1.0 g, blender It was used and mixed to obtain a curable resin composition-4.
[Molding]
The curable resin composition-4 was heat-press molded at 150 ° C. for 5 minutes using a mold having a thickness of 3 mm to obtain a molded product-4.
[Performance measurement]
When the water absorption rate of the molded product-4 was measured, a high water absorption capacity was observed at 16.5% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 92.3 MPa. The results are shown in Table 1.

<Example 5>
[Zeolite surface treatment]
Synthetic zeolite (Molecular sieve 3A powder manufactured by Union Showa Co., Ltd.): Immersed in 100 g of diphenylmethane diisocyanate (MDI): 2.50 g (0.01 mol) in a solution of 500 g of toluene at 50 ° C. for 4 minutes. After that, toluene was removed, and the mixture was further washed with toluene and dried to obtain a surface-treated zeolite-5.
[Preparation of curable resin composition]
Surface-treated zeolite-5: 70 g, unsaturated polyester resin (Showa Denko Corporation, Rigolac 1557): 30 g, peroxide catalyst (Nippon Oil & Fat Co., Ltd., Perbutyl Z): 1.0 g, kneader Was mixed to obtain a curable resin composition-5.
[Molding]
The curable resin composition-5 was heat-press molded 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 product-5 was measured, a high water absorption capacity was observed at 14.0% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 131.7 Pa. The results are shown in Table 1.

<Example 6>
[Zeolite surface treatment]
Synthetic Zeolite (Union Showa Co., Ltd., Molecular Sieve 3A Powder): 100 g, Showa Denko Co., Ltd .: PE-1: 5.44 g (0.01 mol), 2-methacryloyloxyethyl isocyanate (Showa) Karens MOI (manufactured by Denko KK): Immersed in a solution of 2.50 g (0.01 mol) in 500 g of toluene at 40 ° C. for 5 minutes, then removed the toluene, washed with toluene, and dried. Surface-treated zeolite-6 was obtained.
[Preparation of curable resin composition]
Surface-treated zeolite-6: 70 g, acrylic monomer (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., BPE-500): 30 g, peroxide catalyst (manufactured by NOF CORPORATION, perbutyl Z): 1.0 g, Mixing was performed using a blender to obtain a curable resin composition-6.
[Molding]
The curable resin composition-6 was heat-press molded 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 product-6 was measured, a high water absorption capacity was observed at 14.7% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 128.7 MPa. The results are shown in Table 1.

<Example 7>
[Zeolite surface treatment]
Synthetic zeolite in kneader (Union Showa Co., Ltd., Molecular Sieve 3A powder): 100 g and 3-methacryloxypropyltrimethoxysilane (Shinetsu Silicon Co., Ltd., KBM-503): 2.48 g (0. 12 g of styrene in which (01 mol) was dissolved was mixed, stirred and left to stand for 24 hours to obtain surface-treated zeolite / styrene-1.
[Synthesis of vinyl ester]
186 g of bisphenol A type epoxy resin (Epiclon 840 manufactured by DIC Co., Ltd.) is charged in a flask equipped with a stirrer and a reflux tube, and 2,4,6-tris (dimethylaminomethyl) phenol is kept 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 the mixture was cooled at an acid value of 5 to obtain vinyl ester-1.
[Preparation of curable resin composition]
Surface-treated zeolite / styrene-1: 114.48 g in a kneader was mixed with vinyl ester-1: 15 g and perbutyl Z: 0.3 g and stirred with a kneader to obtain a curable resin composition-7 (77% by mass of zeolite). rice field.
[Molding]
The curable resin composition-7 was molded by heating and pressure molding 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 molded product-7 was measured, a high water absorption capacity was observed at 15.1% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 131.3 MPa. The results are shown in Table 1.

<Example 8>
[Simultaneous mixing]
Synthetic zeolite (manufactured by Union Showa Co., Ltd., molecular sieve 3A powder): 100 g, 3-methacryloxypropyltrimethoxysilane (manufactured by Shinetsu Silicon Co., Ltd., KBM-503): 2.48 g (0.01 mol), A mixture of 16 g of styrene, 1:24 g of vinyl ester, and 0.3 g of perbutyl Z: 0.3 g was mixed and stirred, and left at room temperature for 3 days to obtain a curable resin composition-8.
[Molding]
The curable resin composition-8 was heat-press molded 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 product-8 was measured, a high water absorption capacity was observed at 14.2% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 135.9 MPa. 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 HiSiv3000 powder manufactured by Union Showa Co., Ltd. to obtain a curable resin composition-9.
[Molding]
The curable resin composition-9 was heat-press molded 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 product-9 was measured, a high organic substance adsorption capacity was observed at 4.5% by mass, and as a result of measuring the bending strength by JISK7171, the strength was as good as 130.1 MPa. The results are shown in Table 1.

<Comparative Example 1> (Comparison with Example 2)
[Preparation of curable resin composition]
Synthetic zeolite (Union Showa Co., Ltd., molecular sieve 3A powder): 80 g and Mitsubishi Chemical Co., Ltd. as epoxy resin, 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 pressure molding at 150 ° C. for 3 hours using a mold having a thickness of 3 mm to obtain a molded product-2', but there was a portion where the resin did not sufficiently enter. It was a molded product.
[Performance measurement]
When the toluene adsorption rate of the molded product-2'was measured, a high organic substance adsorption capacity was observed at 5.4% by mass, but as a result of the bending strength measurement by JISK7171, the strength was as low as 68.9 MPa. The results are shown in Table 1.

<Comparative Example 2> (Comparison with Example 3)
[Preparation of curable resin composition]
Vinyl ester resin (Showa Denko KK, manufactured by Showa Denko KK, manufactured by adding 1% peroxide catalyst (Perbutyl Z, manufactured by Nippon Oil & Fat Co., Ltd.) to synthetic zeolite (Molecular Sieve 3A powder manufactured by Union Showa Co., Ltd.) When Lipoxy R-804) was mixed using a mortar and attempted high filling, zeolite could only be filled up to 65 Wt%. A curable resin composition-3'was obtained.
[Molding]
The curable resin composition-3'was molded by heating and pressure molding at 120 ° C. for 5 minutes using a mold having a thickness of 3 mm to obtain a molded product-3'.
[Performance measurement]
When the water absorption rate of the molded product-3'was measured, it was 12.5% by mass, which was a lower value than that of Example 3, and as a result of measuring the bending strength by JISK7171, the strength was 93.1 MPa, which was lower than that of Example 3. Met. The results are shown in Table 1.

Claims (12)

A resin composition composed of a surface-treated zeolite and a resin.
The surface treatment includes isocyanate compound treatment and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl)-. A resin composition which is at least one of a thiol compound treatment using at least one thiol compound selected from the group consisting of 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione. .. The resin composition according to claim 1 , wherein the isocyanate compound treatment uses at least one isocyanate compound selected from the group consisting of an isocyanate compound having a (meth) acryloyl group and a polyfunctional isocyanate compound. The resin composition according to claim 1 or 2 , wherein the zeolite is a synthetic zeolite. The crystal structure of the synthetic zeolite, a structure code, LTA type, FAU type, BEA type, LTL type, MFI type, a MWW-type, at least one selected from the group consisting of FER type and MOR type, according to claim 3 The resin composition according to. 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 3. The resin composition according to any one of claims 1 to 5 , wherein the resin is a thermosetting resin. The resin composition according to claim 6 , 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 according to any one of claims 1 to 5 , wherein the resin is a thermoplastic resin. A molded product having adsorptivity, sustained release property, and ion exchange property obtained by molding the resin composition according to any one of claims 1 to 8. A step of mixing and stirring zeolite and a surface treatment agent to apply a surface treatment to the zeolite, and a step of mixing the surface-treated zeolite in the above step with a thermosetting resin and / or a thermoplastic resin to obtain a resin composition. A method for producing a molded product, which comprises a step of molding the resin composition to obtain a molded product having adsorptivity, sustained release property, and ion exchange property.
The surface treatment agent is an isocyanate compound, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl)-. A method for producing a molded product, which is at least one of at least one thiol compound selected from the group consisting of 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione. The step of dissolving the surface treatment agent in a part of at least one of the raw material monomers of the vinyl ester resin and the unsaturated polyester resin, and the surface treatment of the zeolite by immersing the zeolite in the raw material monomer in which the surface treatment agent is dissolved. The step of applying, the step of mixing the residue of at least one of the raw material monomers of the zeolite, the vinyl ester resin, and the unsaturated polyester resin surface-treated in the step to obtain a resin composition, and the step of molding the resin composition. A method for producing a molded product, which comprises a step of obtaining a molded product having adsorptivity, sustained release property, and ion exchange property. A step of simultaneously mixing zeolite, a surface treatment agent, and a thermosetting resin to obtain a resin composition containing surface-treated zeolite, and a molding process of the resin composition for adsorptivity, sustained release, and ion exchange. A method for producing a molded product, which comprises a step of obtaining a molded product having properties.
The surface treatment agent is an isocyanate compound, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl)-. A method for producing a molded product, which is at least one of at least one thiol compound selected from the group consisting of 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.