JP2008069236A - Resin additive and resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin additive having a high mechanical characteristic and also improving discoloration by heating, and a resin composition blended with the same. <P>SOLUTION: This resin additive is characterized by consisting of mesoporous silica derived from the following (A) and (B) components. (A) is a nonionic surfactant, and (B) is a water-soluble silicate monomer expressed by following general formula (1): Si-(OR<SP>1</SP>)<SB>4</SB>[wherein, R<SP>1</SP>is a polyhydric alcohol residue]. The resin composition is characterized by containing the resin additive and a resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin additive and a resin composition containing the same, and particularly to improvement of discoloration by heating in a resin composition having high mechanical properties.

  In modern society, various resins are used as materials for various consumer goods including cosmetic containers. In particular, in consideration of environmental problems on a global scale, in recent years, the use of biodegradable resins, which are resins that can be decomposed in the natural environment, has attracted attention as materials for consumer goods. Such a biodegradable resin is ultimately decomposed into water and carbon dioxide by hydrolysis, microorganisms or enzymes, so that it does not cause bioconcentration and environmental hormone effects, and does not pollute the environment. Are better.

  However, in general, the resin molded product obtained by molding only the resin has insufficient mechanical properties, so that it has been difficult to use it for a portion requiring strength. In addition, the biodegradation rate of the biodegradable resin is not always fast.

  In order to improve the mechanical properties of the resin molded body and to increase the biodegradation rate of the resin, conventionally obtained by ion exchange of the cation of the clay mineral with an organic ion for such a problem. Organically modified clay minerals are used as additives. Here, in many cases, organic onium ions are used as organic ions for ion-exchange of clay minerals.

  For example, as a biodegradable polyester material having excellent mechanical properties, a biodegradable high mechanical property material composed of a polyester mainly composed of lactic acid and a swellable layered silicate is disclosed (see Patent Document 1). ). Here, the swellable layered silicate is, for example, an organic onium ion such as a quaternary ammonium ion in which four mutually independent alkyl groups having 1 to 30 carbon atoms or alkyleneoxy groups are bonded to a nitrogen atom. Silicate treated with

In addition, as a biodegradable resin composition that maintains the rigidity of the biodegradable resin molded body sufficiently high and increases the biodegradation rate, a biodegradable resin and an organic agent dispersed in the biodegradable resin are used. A biodegradable resin composition containing an organized layered clay mineral and having an average particle size of the organized layered clay mineral of 1 μm or less is also disclosed (see Patent Document 2). Here, the organic agent is an organic onium compound such as an organic ammonium compound, an organic phosphonium compound, an organic pyridinium compound, and an organic sulfonium compound containing primary, secondary, tertiary, or quaternary ammonium ions. It is.
JP 2002-338996 A JP 2001-89646 A

  However, a resin composition obtained by adding an organically modified clay mineral obtained by treating with organic onium ions to a resin as described above has insufficient heat resistance. That is, when heated to mold the resin composition, there is a problem that the color of the resin composition changes to yellow regardless of the type of resin.

  The present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is to have a high mechanical property and a resin additive capable of improving discoloration by heating, and a resin composition containing the same To provide things.

  The present inventors conducted extensive research to solve the above-described problems of the prior art. As an additive, mesoporous silica derived from a nonionic surfactant and a water-soluble silicate monomer substituted with a polyhydric alcohol was used. It was found that the resin composition used had high mechanical properties and the discoloration by heating was remarkably improved, and the present invention was completed.

That is, the resin additive according to the present invention is characterized by comprising mesoporous silica derived from the following components (A) and (B).
(A) Nonionic surfactant (B) Water-soluble silicate monomer represented by the following general formula (1) Si- (OR ¹ ) ₄ (1)
(In the formula, R ¹ is a polyhydric alcohol residue.)

The resin additive according to the present invention is characterized by comprising a mesoporous silica composite derived from the components (A) and (B).
The resin additive according to the present invention is characterized by comprising a mesoporous silica outer shell characterized by being derived from the above components (A) and (B).

In the resin additive, (B) R ^{1 of the} water-soluble silicate monomer is ethylene glycol residue, propylene glycol residue, butylene glycol residue, glycerin residue, or ethylene glycol, propylene glycol, butylene glycol, glycerin. Any one of the residues of the condensate is preferred.

Moreover, the resin composition concerning this invention is characterized by including the said resin additive and resin. In the resin composition, it is preferable that the resin is a biodegradable resin. In the resin composition, it is preferable that the biodegradable resin is polylactic acid.
Moreover, the resin molded body concerning this invention was shape | molded using the said resin composition, It is characterized by the above-mentioned.

  By using the resin additive according to the present invention, a resin composition having high mechanical properties and improved discoloration by heating can be obtained.

The resin additive according to the present invention comprises mesoporous silica, mesoporous silica composite, or mesoporous silica outer shell derived from the following components (A) and (B).
(A) Nonionic surfactant (B) Water-soluble silicate monomer represented by the following general formula (1) Si- (OR ¹ ) ₄ (1)
(In the formula, R ¹ is a polyhydric alcohol residue.)

  The nonionic surfactant (A) used in the present invention is not particularly limited, and various nonionic surfactants exemplified below can be used. Typical examples include polyoxyethylene type nonionic surfactants, polyglycerin type nonionic surfactants, sugar ester type nonionic surfactants, etc., and these should be used alone or in combination of two or more. Can do.

  More specifically, for example, POE alkyl ether, POE alkyl phenyl ether, POE / POP alkyl ether, POE fatty acid ester, POE sorbitan fatty acid ester, POE glycerin fatty acid ester, POE castor oil or hydrogenated castor oil derivative, POE beeswax Examples include lanolin derivatives, alkanolamides, POE propylene glycol fatty acid esters, POE alkylamines, POE fatty acid amides, sugar fatty acid esters, polyglycerin fatty acid esters, and polyether-modified silicones. These can be used individually by 1 type or in combination of 2 or more types. “POE” means polyoxyethylene, and “POP” means polyoxypropylene, which may be described as follows.

  In the POE type nonionic surfactant, the alkyl group is an alkyl group of a saturated or unsaturated fatty acid having 6 to 22 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc. In addition to these, mixed fatty acids obtained from nature such as coconut oil fatty acid, beef tallow fatty acid, hydrogenated beef tallow fatty acid, castor oil fatty acid, olive oil fatty acid, palm oil fatty acid, etc. It may be an alkyl group including a fatty acid. Further, the alkyl group may be a fluoroalkyl group in which hydrogen is substituted with fluorine at an arbitrary ratio. In the POE type nonionic surfactant, the POE condensation number is in the range of 1 to 50, more preferably in the range of 5 to 20.

The water-soluble silicate monomer (B) used in the present invention is represented by the above general formula (1). In the water-soluble silicate monomer represented by the general formula (1), R ¹ is a residue of a polyhydric alcohol, and is represented as a form in which one hydroxyl group in the polyhydric alcohol is removed. The water-soluble silicate monomer can usually be prepared by a substitution reaction between tetraalkoxysilane and a polyhydric alcohol, and R ¹ varies depending on the type of polyhydric alcohol used. When ethylene glycol is used, R ¹ becomes —CH ₂ —CH ₂ —OH.

R ¹ in the general formula (1) is, for example, ethylene glycol residue, diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, polyethylene glycol residue, propylene glycol residue, dipropylene glycol residue. , Polypropylene glycol residue, butylene glycol residue, hexylene glycol residue, glycerin residue, diglycerin residue, polyglycerin residue, neopentyl glycol residue, trimethylolpropane residue, pentaerythritol residue, maltitol Examples include residues. Among these, it is preferable that R ¹ is any one of an ethylene glycol residue, a propylene glycol residue, a butylene glycol residue, and a glycerin residue from the viewpoint of use feeling as an external preparation.

More specifically, examples of the water-soluble silicate monomer (B) used in the present invention include Si— (O—CH ₂ —CH ₂ —OH) ₄ , Si— (O—CH ₂ —CH ₂ —CH _{2). -OH) 4, Si- (O-} CH 2 -CH 2 -CHOH-CH 3) 4, Si- (O-CH 2 -CHOH-CH 2 -OH) 4 , and the like.

  The water-soluble silicate monomer (B) used in the present invention can be prepared, for example, by reacting a tetraalkoxysilane and a polyhydric alcohol in the presence of a solid catalyst.

  The tetraalkoxysilane is not particularly limited as long as four alkoxy groups are bonded to a silicon atom. Examples of the tetraalkoxysilane used for the production of the water-soluble silicate monomer include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Of these, tetraethoxysilane is most preferable from the viewpoint of availability and safety of reaction by-products.

  As an alternative compound of tetraalkoxysilane, mono, di, or trihalogenated alkoxysilane such as monochlorotriethoxysilane, dichlorodimethoxysilane, monobromotriethoxysilane, or the like, or tetrahalogenated silane such as tetrachlorosilane or the like may be used. However, since these compounds produce strong acids such as hydrogen chloride and hydrogen bromide in the reaction with polyhydric alcohols, corrosion of the reactor occurs, and separation and removal after the reaction are difficult. Therefore, it is hard to say that it is practical.

  The polyhydric alcohol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. Examples of the polyhydric alcohol used in the production of the water-soluble silicate monomer include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, and glycerin. , Diglycerin, polyglycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, maltitol and the like. Among these, it is preferable to use any of ethylene glycol, propylene glycol, butylene glycol, and glycerin.

  The solid catalyst is a solid catalyst that is insoluble in the raw material components, reaction solvent, and reaction product to be used, and has an acid site and / or a base site having activity for a substituent exchange reaction on a silicon atom. What is necessary is just solid. Examples of the solid catalyst used in the present invention include an ion exchange resin and various inorganic solid acid / base catalysts.

  Examples of the ion exchange resin used as the solid catalyst include acidic cation exchange resins and basic anion exchange resins. Examples of the resin that forms the base of these ion exchange resins include styrene-based, acrylic-based, and methacrylic-based resins, and functional groups that exhibit catalytic activity include sulfonic acid, acrylic acid, methacrylic acid, quaternary ammonium, And secondary amines. The substrate structure of the ion exchange resin can be selected from a gel type, a porous type, a bipolar type, and the like according to the purpose.

  Examples of the acidic cation exchange resin include Amberlite IRC76, FPC3500, IRC748, IRB120B Na, IR124 Na, 200CT Na (above, manufactured by Rohm and Haas), Diaion SK1B, PK208 (above, manufactured by Mitsubishi Chemical Corporation), Dow EX monosphere 650C, Marathon C, HCR-S, Marathon MSC (above, manufactured by Dow Chemical Co., Ltd.) and the like. Examples of the basic anion exchange resin include Amberlite IRA400J CL, IRA402BL CL, IRA410J CL, IRA411 CL, IRA458RF CL, IRA900J CL, IRA910CT CL, IRA67, IRA96SB (above, manufactured by Rohm and Haas), Dia Ion SA10A, SAF11AL, SAF12A, PAF308L (manufactured by Mitsubishi Chemical Corporation), Dow EX monosphere 550A, marathon A, marathon A2, marathon MSA (manufactured by Dow Chemical Company) and the like.

The inorganic solid acid / base catalyst used as the solid catalyst is not particularly limited. Examples of the inorganic solid acid catalyst include single metal oxides such as Al ₂ O ₃ , SiO ₂ , ZrO ₂ , TiO ₂ , ZnO, MgO, Cr ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO _2. , SiO ₂ —ZrO ₂ , TiO ₂ —ZrO ₂ , ZnO—Al ₂ O ₃ , Cr ₂ O ₃ —Al ₂ O 3, SiO ₂ —MgO, ZnO—SiO _{2 and} other complex metal oxides, NiSO ₄ , FeSO ₄ or the like of metal sulfates, metal phosphates such as _{FePO 4, H 2 SO 4 /} SiO 2 or the like immobilized sulfuric _acid, H ₂ PO 4 / SiO ₂ or the like immobilized phosphoric _acid, H ₃ BO ₃ / SiO ₂ immobilization boric acid etc., activated clay, zeolite, kaolin, natural mineral or layered compounds such as montmorillonite, AlPO ₄ - synthetic zeolites such as _{zeolite, H 3 PW 12 O 40 ·} 5H 2 , Such heteropoly acids such as _H 3 _PW 12 _{O 40} and the like. Examples of the inorganic solid base catalyst include single metal oxides such as Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, MgO, CaO, SrO, BaO, La ₂ O ₃ , ZrO ₃ , and ThO ₃ . , Na ₂ CO ₃ , K ₂ CO ₃ , KHCO ₃ , KNaCO ₃ , CaCO ₃ , SrCO ₃ , BaCO ₃ , (NH ₄ ) ₂ CO ₃ , Na ₂ WO ₄ .2H ₂ O, metal salt such as KCN, Na -Al ₂ O _3, K-SiO alkali metal supported metal oxide such as _2, Na-alkali metal-loaded zeolite such as _{mordenite, SiO 2 -MgO, SiO 2 -CaO} , SiO 2 -SrO, SiO 2 -ZnO, SiO _{2 -Al 2 O 3, SiO 2} -ThO 2, SiO 2 -TiO 2, SiO 2 -ZrO 2, SiO 2 -MoO 3, SiO 2 -WO, Al 2 O ₃ —MgO, Al ₂ O ₃ —ThO ₂ , Al ₂ O ₃ —TiO ₂ , Al ₂ O ₃ —ZrO ₂ , ZrO ₂ —ZnO, ZrO ₂ —TiO ₂ , TiO ₂ —MgO, ZrO ₂ —SnO ₂ And composite metal oxides.

  The solid catalyst can be easily separated from the product by a treatment such as filtration or decantation after completion of the reaction.

  In the production of the water-soluble silicate monomer, the temperature condition during the reaction is not particularly limited, but it is preferably performed under a temperature condition of 5 to 90 ° C. When the reaction is carried out at a temperature exceeding 90 ° C., there are problems in practical use such as durability of the reaction apparatus, and it is necessary to use a high boiling point solvent as a reaction solvent, which makes it difficult to completely separate and remove the solvent. Become. Moreover, in the manufacturing method of this invention, it is more suitable to react on normal temperature conditions, ie, temperature conditions of 5-35 degreeC. Here, when the reaction is performed at room temperature, it is preferable to use any one of ethylene glycol, propylene glycol, and butylene glycol as the polyhydric alcohol. When other polyhydric alcohols such as glycerin are used, a reaction product may not be produced under normal temperature conditions.

  In the production of the water-soluble silicate monomer, a solvent may not be used during the reaction, but various solvents may be used as necessary. The solvent used in the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate, methyl acetate, acetone, methyl ethyl ketone, cellosolve, diethyl ether and dioxane, ethers, and the like. , Ketone solvents, polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide, and halogen solvents such as chloroform and dichloromethane. Here, in order to suppress the hydrolysis and condensation reaction of the tetraalkoxysilane used as a raw material, the solvent is preferably dehydrated in advance. Among these, it is preferable to use acetonitrile, toluene, or the like that can accelerate the reaction by forming an azeotrope with an alcohol such as ethanol that is by-produced during the reaction and removing it from the system.

  The mesoporous silica, mesoporous silica composite, or mesoporous silica outer shell used as the resin additive according to the present invention is derived from the above components (A) and (B). Hereinafter, these manufacturing methods will be described.

  In the present invention, first, a mesoporous silica composite is produced using the components (A) and (B). As a method for producing the mesoporous silica composite, a method of mixing ordinary components (A) and (B) in a solvent can be used. In this method, a mesoporous silica composite is usually produced by mixing the component (A) in a solvent and mixing the component (B), and then standing or stirring at a predetermined temperature for a predetermined time.

  As the solvent used for the production of the mesoporous silica composite, usually, water or a solvent containing a mixture of an organic solvent compatible with this and water can be used, and the nonionic surfactant of component (A) From the viewpoint of promoting the formation of self-organization, preferably water alone or a mixed solvent with various alcohols for improving the solubility of the nonionic surfactant, more preferably water alone, water-ethanol or water- It is a mixed solvent of methanol.

  Although the temperature conditions for producing the mesoporous silica composite are not particularly limited, it is usually carried out in the range of room temperature to the boiling temperature of the solvent used. From the viewpoint of mixing and promoting the reaction, the component (A ) Nonionic surfactant is produced in a temperature range in which an aggregate is stably formed. When the nonionic surfactant (A) to be used exhibits a cloud temperature that is the kraft temperature corresponding to the melting point of the hydrate or the solubilization limit temperature of the nonionic surfactant micelle, the cloud point is higher than the kraft temperature. The following temperatures are preferred.

  The reaction time in the production of the mesoporous silica composite is usually in the range of 1 minute to 168 hours, preferably 5 minutes to 48 hours, more preferably from the viewpoint of hydrolysis and condensation polymerization of the silicate monomer. 30 minutes to 10 hours.

  The production of the mesoporous silica composite in the present invention is carried out under neutral conditions, specifically within the range of pH 4 to 10, particularly preferably pH 6 to 8. Further, from the viewpoint of promoting the hydrolysis and polycondensation of the silicate monomer without forming an electrolyte as a by-product, the components (A) and (B) are dissolved in water or a water-alcohol mixed solvent. In addition, for the purpose of accelerating the reaction between the components (A) and (B), it is possible to add an acid or a base as in the production of mesoporous silica by a normal template method. Depending on the intended use of the mesoporous silica, it is necessary to remove the electrolyte by washing.

  In the production of the mesoporous silica composite in the present invention, the nonionic surfactant of component (A) may be used alone or in combination of two or more, and the concentration is particularly limited as long as a three-dimensional micelle structure is formed. Although it is not a thing, the density | concentration in a solution is 0.01 to 80 weight% normally, Preferably it is 0.2 to 30 weight%, More preferably, it is 1.0 to 20.0 weight%.

  In the production of the mesoporous silica composite in the present invention, the ratio of the component (B) to the sum of the components (A) and (B) of the water-soluble silicate monomer is usually 0.1 to 98 mol%, preferably 1 to 95 mol. %, More preferably 10 to 90 mol%.

  The production confirmation of the mesoporous silica composite produced as described above can be performed by observation with a scanning or transmission electron microscope, powder X-ray diffraction, or the like.

  By further washing the mesoporous silica composite obtained as described above with an acidic aqueous solution, water, an organic solvent compatible with water or an aqueous solution thereof, a mesoporous silica outer shell can be produced.

  The processing solvent used in the production of the mesoporous silica outer shell is not particularly limited, and various solvents can be used. From the viewpoint of maintaining the structure of the mesoporous silica outer shell, it is preferably a polar solvent. More preferably, it is water or alcohol.

  The processing temperature in the production of the mesoporous silica shell is usually performed in the range of room temperature to the boiling temperature of the solvent used, but the structure retention of the mesoporous silica shell, the yield of the mesoporous silica shell, and the boiling point of the processing solvent. In view of the above, it is preferably room temperature to 100 ° C, more preferably room temperature to 80 ° C.

  The treatment time for producing the mesoporous silica outer shell is usually in the range of 1 to 72 hours. From the viewpoint of maintaining the structure of the mesoporous silica outer shell and the yield of the mesoporous silica outer shell, it is preferably 8 to 48 hours. Yes, more preferably 24 to 48 hours.

  The treatment pH during the production of the mesoporous silica outer shell is usually performed in the range of 0 to 4, preferably 0 to 2 from the viewpoint of maintaining the structure of the mesoporous silica outer shell and the yield of the mesoporous silica outer shell, More preferably, it is 0-1.

  The acid used for the treatment in the production of the mesoporous silica outer shell is not particularly limited, and various acids that are usually present can be used. For example, hydrochloric acid, acetic acid, nitric acid, sulfuric acid, oxalic acid and phosphoric acid. From the viewpoint of the yield of mesoporous silica outer shell, preferred are hydrochloric acid, acetic acid, nitric acid and sulfuric acid, and more preferred are hydrochloric acid and acetic acid.

  Confirmation of the mesoporous silica outer shell produced as described above can be performed by powder X-ray diffraction, nitrogen adsorption / desorption measurement, electron microscope observation, and the like.

  The mesoporous silica according to the present invention can be produced by firing the mesoporous silica composite or mesoporous silica outer shell obtained as described above.

  The calcination temperature in the production of mesoporous silica is usually in the range of 300 to 900 ° C., but preferably 400 to 650 ° C., more preferably from the viewpoint of maintaining the structure of mesoporous silica and completely removing the surfactant. Is 500-600 ° C

  The calcination time in the production of mesoporous silica is usually performed in the range of 2 to 24 hours, but is preferably 4 to 12 hours, more preferably 6 to 10 hours, from the viewpoint of complete removal of the surfactant. is there.

  The mesoporous silica composite, mesoporous silica outer shell, and mesoporous silica produced as described above can be used alone as a resin additive, and if there is no problem, these two or three kinds can be used. Can be used simultaneously as a resin additive.

  The resin additive according to the present invention comprises mesoporous silica, mesoporous silica composite, or mesoporous silica outer shell produced as described above. In the resin composition according to the present invention, the resin additive And a resin. In the resin composition according to the present invention, the ratio of the resin additive to the resin is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass. When the ratio of the resin additive to the resin is less than 0.1% by mass, the mechanical properties of the resin molded body may be insufficient. On the other hand, when the ratio of the resin additive to the resin exceeds 20% by mass, the cost of the resin composition increases.

  Moreover, arbitrary resin can be used as resin used for the resin composition concerning this invention. That is, the resin contained in the resin composition according to the present invention may be a biodegradable resin or a non-biodegradable resin. However, the biodegradable resin is ultimately decomposed into water and carbon dioxide by hydrolysis, microorganisms or enzymes, and does not cause bioconcentration and environmental hormonal effects, and can reduce environmental pollution. As the resin used in the resin composition according to the present invention, a biodegradable resin is preferably used.

  The biodegradable resin used in the resin composition according to the present invention is not particularly limited as long as it is a resin that can be decomposed or reduced in molecular weight by microorganisms or enzymes, and examples thereof include polyester resins, polyester amide resins, and polyester carbonates. Resin, polysaccharide (polysaccharide), polypeptide, lignin, and derivatives thereof.

  Polyester resins include at least one diol such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, decamethylene glycol, and neopentyl glycol, and succinic acid, adipic acid, suberic acid, and sebacin. And aliphatic polyesters and aliphatic polyester copolymers obtained by polycondensation reaction with at least one aliphatic dicarboxylic acid such as acids, dodecanedioic acid and anhydrides thereof, and mixtures thereof. Examples of the above aliphatic polyesters include poly (ethylene succinate), poly (butylene succinate), poly (hexamethylene succinate), poly (ethylene adipate), poly (butylene adipate), poly (hexamethylene adipate) , Poly (ethylene oxalate), poly (butylene oxalate), poly (hexamethylene oxalate), poly (ethylene sebacate), and poly (butylene sebacate). An example of the aliphatic polyester copolymer is poly (butylene succinate-co-butylene adipate).

  In addition to the diol, a polyol having three or more hydroxyl groups may be used. In addition to the aliphatic dicarboxylic acid, an aromatic dicarboxylic acid and / or a polycarboxylic acid having three or more carboxyl groups is used. Also good. Examples of the polyester resin obtained by the polycondensation reaction of diol and aromatic dicarboxylic acid include poly (butylene succinate-co-butylene terephthalate) and poly (butylene adipate-co-butylene terephthalate).

  The polyester resin also includes poly (hydroxy acid) and copolymers thereof. Examples of poly (hydroxy acids) include polylactic acid, polyglycolic acid, poly (ε-caprolactone), poly (β-prochiolactone), poly (δ-valerolactone), poly (3-hydroxyvalerate), Poly (3-hydroxybutyrate) and poly (3-hydroxycaprate) are mentioned.

  Examples of the polysaccharide include cellulose, hemicellulose, chitin, and chitosan. These polysaccharides may be derivatives of polysaccharides in which at least a part of the molecule is substituted with another chemical substance, or another chemical substance is added to at least a part of the molecule. Examples of the cellulose derivative include methyl cellulose and carboxymethyl cellulose.

  Examples of the polypeptide include collagen and collagen derivatives.

  The lignin may be a phenylpropane skeleton resin obtained from a wooded plant and a derivative thereof, and the isolation method is not limited.

  Polyester resins, polyester amide resins, polyester carbonate resins, polysaccharides (polysaccharides), polypeptides, lignin, and derivatives thereof may be used alone or in combination.

  Among the biodegradable resins described above, polylactic acid is easily obtained because its raw material is derived from a plant (such as corn). Therefore, if polylactic acid is used as the material of the resin molded body, the resin molded body can be easily and inexpensively manufactured. Polylactic acid is also excellent in terms of transparency and stability.

  Non-biodegradable resins used in the resin composition according to the present invention include polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl acetate, and vinyl such as polystyrene. Polymers, polyamides, polyesters excluding the above-mentioned biodegradable polyester-based resins, polycarbonates, polybutadienes, butadiene / styrene copolymers, ethylene / propylene copolymers, butadiene / acrylonitrile copolymers, and ethylene / propylene / Vinyl copolymers such as diene copolymers, natural rubber, acrylic rubber, chlorinated butyl rubber, elastomers such as chlorinated polyethylene, or acid-modified products thereof such as maleic anhydride, styrene / maleic anhydride copolymers The sti On / phenylmaleimide copolymer, polyacetal, polysulfone, phenoxy resin, polyphenylene sulfide, polyphenylene ether, polyether sulfone, polyether ketone, polymethyl methacrylate, and the like polyarylate and the like.

  It continues and demonstrates the manufacturing method of the resin composition concerning this invention. The resin composition concerning this invention can be obtained by melt-kneading the resin additive concerning this invention, desired resin, and another additive as needed in a predetermined ratio. This melt-kneading is performed by heating to a temperature higher than the melting point or softening point of the resin. In practice, melt kneading may be performed by using a general kneader such as a single screw extruder, a twin screw extruder, a roll kneader, and a Brabender. In order to uniformly disperse the agent in the resin, it is preferable to use a twin screw extruder. Moreover, regarding the resin composition according to the present invention, the dispersibility of the resin additive in the resin can be confirmed by observing the resin composition using an electron microscope.

  Moreover, the resin composition concerning this invention can be manufactured also by the well-known interlayer polymerization method. That is, the resin additive according to the present invention and a monomer capable of forming a desired resin are mixed at a predetermined ratio, and the above monomer is polymerized by a method such as heating in the presence of an appropriate catalyst. Thus, by polymerizing the above monomers to form a desired resin, a resin composition in which a resin additive is dispersed in the desired resin can be obtained.

  For example, when a resin composition in which the resin additive of the present invention is dispersed in polylactic acid is produced by an interlayer polymerization method, the resin additive of the present invention is added to lactide which is a dimer of lactic acid as a monomer of polylactic acid. And a small amount of tin octylate as a polymerization catalyst is added to the mixture. Thereafter, a mixture of lactide, resin additive, and tin octylate is heated at a temperature of about 160 ° C. to polymerize lactide to form polylactic acid, and the resin composition in which the resin additive is dispersed in polylactic acid You can get things. In addition, since the resin additive of this invention contained in the resin composition concerning this invention does not contain an ammonium ion, it does not reduce the activity of the tin octylate of a catalyst. For this reason, in this invention, an interlayer polymerization method can be used suitably as a manufacturing method of the resin composition containing polylactic acid and a resin additive.

  Next, the manufacturing method of the resin molding concerning this invention is demonstrated easily. The resin molded body according to the present invention is obtained by molding the resin composition according to the present invention by at least one molding method known in the art of injection molding, blow molding, extrusion molding, vacuum molding, pressure molding, and inflation molding. It is done.

  The resin molded body according to the present invention can be widely used as a consumer goods including cosmetic containers and other durable materials. Specific examples of the resin molded body according to the present invention include, for example, household goods, packaging containers, and electrical and electronic equipment casings as injection molded bodies; containers of fluids such as beverages or cosmetics, foods as blow molded bodies Or containers for chemicals and tanks for fuel, etc .; Extrusion molded materials include deep drawing sheet, batch type foam sheet, credit cards and other cards, underlays and clear files Or agricultural and industrial films and sheets, and pipes such as straws and hard pipes for agriculture or horticulture; as vacuum molded bodies or compressed air molded bodies, fresh food trays, instant food containers, fast food containers, and lunch boxes And the like, blister pack containers for product display, and press-through pack containers for chemicals.

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

First, a method for producing the water-soluble silicate monomer used in the present invention will be described.
Synthesis example 1
20.8 g (0.1 mol) of tetraethoxysilane and 24.9 g (0.4 mol) of ethylene glycol were added to 150 ml of acetonitrile, and a strongly acidic ion exchange resin (DowEX 50W-X8: Dow) was used as a solid catalyst. (Chemical Co., Ltd.) After adding 1.8 g, the mixture was stirred at room temperature. Initially, the reaction solution separated into two layers was uniformly dissolved after about one hour. Then, after stirring for 5 days, the solid catalyst was separated by filtration, and acetonitrile was distilled off under reduced pressure to obtain 39 g of a transparent viscous liquid. As a result of NMR analysis, it was confirmed that the product was the target (tetra (2-hydroxyethoxy) silane) (yield: 72.5%).

It continues and demonstrates the manufacturing method of the resin additive (mesoporous silica) concerning this invention.
Example 1
Ion exchanged water (270 g) and surfactant POE (10 mol) cholesterol ether (15 g) were mixed and stirred until uniform. When tetra (2-hydroxyethoxy) silane (15 g) was added to this solution and allowed to stand at 60 ° C. for 24 hours, silica was generated from the solution and precipitated. The silica obtained by filtration was allowed to stand at 90 ° C. for 24 hours and dried, and then ethanol was added and stirred overnight at room temperature. After removing the ethanol solution containing the surfactant, the mixture was allowed to stand at 80 ° C. for 5 hours, and the ethanol was removed to obtain silica powder (3.0 g).

  The silica powder obtained in Example 1 was observed with a transmission electron microscope. A photograph is shown in FIG. As shown in FIG. 1, sheet-like mesoporous silica having a regular pore structure was obtained.

Resin composition 1
8 g of the mesoporous silica powder obtained in Example 1 was added to 100 g of polylactic acid, and heated and melt-kneaded to obtain a resin composition 1. In addition, the inorganic content in the resin composition 1 is 4.5 mass%.

  The resin composition 1 obtained as described above was observed with an electron microscope. A photograph is shown in FIG. As shown in FIG. 2, in the resin composition 1, mesoporous silica (nanometer size) smaller than 1 μm is uniformly dispersed in polylactic acid, and the resin composition 1 is a polymer nanocomposite. I was able to confirm that.

Subsequently, the elastic modulus as a mechanical property of the resin composition 1 was measured. As a result, the elastic modulus of the resin composition 1 was 4.4 × 10 ⁹ Pa.

  Furthermore, as a result of visually evaluating the color of the resin composition 1, the color of the resin composition 1 was colorless and transparent.

Comparative resin composition 1 (resin only)
As a comparative example for the resin composition 1 of the present invention, polylactic acid containing no additive was used, and a test similar to the present invention was performed as the comparative resin composition 1.

As a result, the elastic modulus of polylactic acid was 4.0 × 10 ⁹ Pa. Moreover, as a result of visually evaluating the color of polylactic acid, the color of polylactic acid was colorless and transparent.

Comparative resin composition 2 (with organically modified viscosity mineral added)
As a comparative example for the resin composition 1 of the present invention, 4 g of an organically modified clay mineral obtained by ion exchange of a cation of a clay mineral with a quaternary ammonium ion was heated and melt-kneaded with 100 g of polylactic acid, and the comparative resin composition 2 Manufactured. In addition, this organic modified clay mineral is a salt (trade name ESO CARD C12: Lion Akzo) containing an inorganic cation of synthetic fluorine mica (trade name ME100: manufactured by Coop Chemical Co., Ltd.) and dodecyl = bis (hydroxyethyl) = methylammonium ion. It is an organically modified clay mineral obtained by ion exchange using In addition, the inorganic content in the comparative resin composition 2 is 3 mass%. A test similar to the present invention was performed on the comparative resin composition 2 produced as described above.

As a result, the elastic modulus of the comparative resin composition 2 was 4.2 × 10 ⁹ Pa. Moreover, as a result of visually evaluating the color of the comparative resin composition 2, the color of the composition was yellow.

  From the above results, when the elastic modulus as the mechanical property of the resin composition 1 of the present invention is compared with the elastic modulus of the comparative resin composition 1, the elastic modulus of the resin composition 1 of the present invention is the comparative resin composition 1. It was larger than the elastic modulus. Moreover, when compared with the elastic modulus of the comparative resin composition 2, when the inorganic content is uniform, the elastic modulus is comparable, and the resin composition 1 of the present invention is a comparative resin using an organically modified viscosity mineral. It was confirmed that it had the same mechanical properties as the composition 2.

  Further, when the results of visual evaluation of the colors of the resin composition 1 of the present invention and the comparative resin compositions 1 and 2 were compared, the color of the comparative resin composition 2 (addition of organically modified viscosity mineral) was yellow. The colors of the resin composition 1 of the present invention and the comparative resin composition 1 (resin only) were colorless and transparent. Therefore, since the resin composition 1 of the present invention had little yellowness and was close to the color of only the resin not subjected to the heating and melting step, it was confirmed that the resin was hardly discolored by the heating and melting step.

It is an electron micrograph of the resin additive (Example 1) concerning this invention. It is an electron micrograph of the resin composition (resin composition 1) concerning this invention.

Claims (8)

A resin additive comprising mesoporous silica derived from the following components (A) and (B):
(A) Nonionic surfactant (B) Water-soluble silicate monomer represented by the following general formula (1) Si- (OR ¹ ) ₄ (1)
(In the formula, R ¹ is a polyhydric alcohol residue.)   A resin additive comprising a mesoporous silica composite derived from the components (A) and (B).   A resin additive comprising a mesoporous silica outer shell derived from the components (A) and (B). In the resin additive according to any one of claims 1 to 3, (B) R ¹ is an ethylene glycol residue of the water-soluble silicate monomers, propylene glycol residue, a butylene glycol residue, glycerol residue or ethylene glycol, A resin additive characterized by being one of the residues of a condensate of propylene glycol, butylene glycol and glycerin.   A resin composition comprising the resin additive according to claim 1 and a resin.   The resin composition according to claim 5, wherein the resin is a biodegradable resin.   7. The resin composition according to claim 6, wherein the biodegradable resin is polylactic acid.   A resin molded product, which is molded using the resin composition according to claim 5.