JP5789486B2 - Resin modifier - Google Patents

Description

  The present invention is a resin modifier that is excellent in phase solubility with an amorphous resin or a crystalline resin and improves the molding processability, physical properties, flexibility, impact resistance, etc. It is related with the resin modifier excellent in thermal stability which can suppress coloring by.

  As a resin modifier, sucrose benzoate is known, and it is possible to improve molding processability and physical properties of amorphous resin such as ABS resin, polyvinyl chloride resin, epoxy resin, unsaturated polyester resin, It is known to improve the flexibility and impact resistance of conductive polyester (Patent Documents 1 and 2).

  However, since sucrose benzoate is a sucrose derivative, when it is added as a modifier, there is a problem in the hue of products made of these resins and the thermal stability of the hue. That is, sucrose benzoate is generally produced using an organic solvent, but first, coloring occurs in the heating process for removing the organic solvent in the production process. The degree of coloring tends to become more prominent as the proportion of components having a low degree of esterification (average degree of substitution) in sucrose benzoate increases. In addition, if we try to shorten the processing time using special processing equipment (for example, a thin film distillation apparatus) and suppress the thermal history of sucrose benzoate when removing the organic solvent, the coloring is suppressed as much as possible. However, after adding sucrose benzoate to the resin, there is a problem that coloring occurs due to a heat history when the resin is processed and molded.

  For this reason, sucrose benzoate is never satisfactory as a resin modifier that requires optical transparency, and development of a sugar derivative with high heat resistance instead of this has been desired.

JP-A-52-81362 JP 62-15582 A

  The present invention is a resin modifier that is excellent in phase solubility with an amorphous resin or a crystalline resin and improves the molding processability, physical properties, flexibility, impact resistance, etc. It is an object of the present invention to provide a resin modifier excellent in thermal stability that can suppress coloring due to.

  As a result of diligent research aimed at solving the above problems, the present inventors have found that when an ester of a specific disaccharide and a specific aromatic monocarboxylic acid is used, compared to sucrose benzoate, an equivalent heat The present inventors have found that coloring upon receiving a history can be suppressed, and further studied and completed the present invention.

（式中、Ｒ¹〜Ｒ⁵は、独立に、水素原子、アルキル基およびアルコキシ基から選択される基である。但し、二糖がショ糖の場合は、Ｒ¹〜Ｒ⁵の少なくとも一つがアルキル基またはアルコキシ基である。）
で示される芳香族モノカルボン酸とのエステルを含んでなる樹脂改質剤、
［２］前記二糖が、ショ糖および／またはマルチトールである上記［１］記載の樹脂改質剤、
［３］ショ糖トルイル酸エステル、マルチトール安息香酸エステルおよび／またはマルチトールトルイル酸エステルを含んでなる樹脂改質剤、
に関する。 That is, the present invention
[1] Disaccharide and general formula (I)

(In the formula, R ^{1 to} R ⁵ are independently a group selected from a hydrogen atom, an alkyl group and an alkoxy group. However, when the disaccharide is sucrose, at least one of R ^{1 to} R ⁵ is An alkyl group or an alkoxy group.)
A resin modifier comprising an ester with an aromatic monocarboxylic acid represented by
[2] The resin modifier according to the above [1], wherein the disaccharide is sucrose and / or maltitol,
[3] Resin modifier comprising sucrose toluic acid ester, maltitol benzoic acid ester and / or maltitol toluic acid ester,
About.

  The resin modifier of the present invention is excellent in phase solubility with an amorphous resin or a crystalline resin, and can improve molding processability, physical properties, flexibility, impact resistance, etc. It also has the excellent feature of being able to suppress coloring. Therefore, it can be used as a modifier for resins that require optical transparency.

  The resin modifier of the present invention has an average value of the esterification rate of the alcohol portion of the disaccharide with an aromatic monocarboxylic acid (hereinafter referred to as “average ester substitution degree” or “average substitution degree”). Even if it is low, it also has the feature of exhibiting excellent thermal stability.

  The resin modifier of the present invention comprises an ester of a disaccharide and an aromatic monocarboxylic acid (I).

  Here, the disaccharide is preferably a disaccharide having at least one of a pyranose structure or a furanose structure, such as sucrose, trehalose, isotrehalose, neotrehalose, galactosucrose, maltitol, lactitol, etc. Non-reducing sugars are preferred, and sucrose or maltitol is preferred. 1 type (s) or 2 or more types can be used for this disaccharide.

In the aromatic monocarboxylic acid (I), when the disaccharide is sucrose, at least one of R ^{1 to} R ⁵ is preferably an alkyl group, of which one (preferably R ³ ) is preferably an alkyl group and the remainder being a hydrogen atom. On the other hand, when the disaccharide is another sugar, R ^{1 to} R ⁵ are each independently preferably a hydrogen atom or an alkyl group, and benzoic acid or all of which are all hydrogen atoms (preferably R ³ ) is more preferably an alkyl group and the remainder is a hydrogen atom.

  Although the ester according to the present invention exhibits excellent thermal stability even when the average degree of substitution is low, the preferred average degree of substitution is 2.5 to 7.9, preferably 3.0 to 7. 9 is given. When the average degree of substitution is lower than 2.5, the content of unreacted sucrose tends to increase, and industrial production efficiency tends to deteriorate. When the average degree of substitution is higher than 7.9, Production tends to be difficult.

  The ester according to the present invention can be produced by a conventional method, for example, according to the method for producing sucrose benzoate described in JP-A No. 61-4839.

  That is, it can be produced by subjecting a disaccharide as a raw material and a chloride of an aromatic monocarboxylic acid to an esterification reaction in a mixed solution of a hydrophilic solvent and water in the presence of an alkaline compound. Suitable hydrophilic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ether solvents such as dioxane and tetrahydrofuran, ester solvents such as methyl acetate, and alcohol solvents such as tertiary butanol. Can be used.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, trimethylamine, and triethylamine.

  The mixing ratio of the hydrophilic solvent and water is preferably such that the water content of the uniform liquid layer composed of both is 7 to 80%. This is because these hydrophilic solvents dissolve the aromatic monocarboxylic acid chloride or product ester, which is one of the raw materials, but the other disaccharide, which is the other raw material, does not dissolve at all or reacts. From the point of view of efficiency, it can only be dissolved to the extent that it is not practically used. By mixing water, which is a good solvent for disaccharides, the mixed solution can dissolve the disaccharides that are practically used. It is. Therefore, by utilizing such properties of the hydrophilic solvent, the reaction rate of the disaccharide and the aromatic monocarboxylic acid chloride can be regulated, and as a result, the disaccharide / aromatic monocarboxylic acid chloride Depending on the charged amount (molar ratio), esters having different degrees of substitution can be produced.

  The reaction is carried out by dissolving or suspending a disaccharide and an aromatic monocarboxylic acid chloride in a mixture of a hydrophilic solvent and water, and adding an equivalent amount or a slight excess of an alkaline compound to the aromatic monocarboxylic acid chloride. Add or drop disaccharides and alkaline compounds in a mixed solution or add aromatic monocarboxylic acid chloride dropwise, or dissolve or suspend disaccharides in a mixed solvent to form an aromatic monocarboxylic acid salt. The product and the alkaline compound can be dropped simultaneously or alternately.

  Although reaction temperature can be employ | adopted to -15 degreeC-100 degreeC, More preferably, it is -10 degreeC-30 degreeC. However, after all the reaction raw materials have been dropped, the reaction may be completed in a high temperature range in order to promote the completion of the reaction.

  It is desirable to keep the pH during the reaction weakly alkaline. On the other hand, under strong alkalinity (for example, pH 13 or higher depending on the reaction temperature, etc.), the side reaction of hydrolysis of the aromatic monocarboxylic acid is remarkable.

  The reaction time is not particularly limited as long as the reaction between the raw materials can sufficiently complete the reaction. Although the specific time depends on the amount of the raw material compound and various conditions, it is usually sufficient to perform for about 1 hour.

  Examples of the resin to which the modifying agent is added include amorphous resins such as ABS resin, polyvinyl chloride resin, epoxy resin, and unsaturated polyester, and crystalline resins such as crystalline polyester resin. Resin can be suitably selected according to the use. Further, as the modifier of the present invention to be added to the resin, a more appropriate one can be appropriately selected according to the kind and use of the resin.

  The ABS resin is not particularly limited. For example, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, chlorinated polyethylene, acrylic rubber (for example, methyl acrylate, ethyl acrylate, Butyl acrylate, etc.) and acrylonitrile, styrene, acrylic acid, acrylic acid amide, 2-chloroethyl vinyl ether, and other rubbery polymers such as acrylonitrile, styrene, α-methylstyrene, methacrylic acid Examples thereof include those obtained by graft polymerization of methyl and the like, and further include acrylonitrile-polybutadiene-styrene graft copolymers. ABS resin may be used individually by 1 type, and may use 2 or more types together.

  The polyvinyl chloride resin is not particularly limited, and for example, vinyl chloride homopolymer resin, chlorinated vinyl chloride resin, one or more monomers copolymerizable with vinyl chloride monomer, A vinyl chloride copolymer resin (for example, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) obtained by random copolymerization or block copolymerization, or a functional group such as a hydroxyl group is grafted to the above resin. And a resin obtained by reacting such a functional group with a reactive compound and graft-bonding them. A polyvinyl chloride resin may be used individually by 1 type, and may use 2 or more types together.

  The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, phenol biphenyl aralkyl epoxy resin. Aralkyl type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, anthracene type epoxy resins, condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups Examples include epoxidized products, triglycidyl isocyanurate, and alicyclic epoxy resins. An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

  The unsaturated polyester resin is not particularly limited. For example, the unsaturated polyester resin is synthesized by addition reaction or dehydration condensation reaction of α, β-olefinic unsaturated dicarboxylic acid or its anhydride and glycol. Further, saturated dicarboxylic acids, aromatic dicarboxylic acids or anhydrides thereof, or dicyclopentadiene that reacts with carboxylic acids can be used in combination. Examples of the α, β-olefin unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these dicarboxylic acids. Examples of dicarboxylic acids used in combination with these α, β-olefinic unsaturated dicarboxylic acids include, for example, adipic acid, sebacic acid, succinic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid And tetrachlorophthalic acid. Among these, it is preferable to use fumaric acid as the α, β-olefinic unsaturated dicarboxylic acid and isophthalic acid as the dicarboxylic acid. An unsaturated polyester resin may be used individually by 1 type, and may use 2 or more types together.

  The crystalline polyester resin is not particularly limited. For example, polyethylene terephthalate, poly-1,4-butylene terephthalate, polyethylene-2,6-naphthalate, polycyclohexanedimethanol terephthalate, poly-1,4-butylene. Examples thereof include crystalline polyesters such as diphenyl-4,4′-dicarboxylate, polyethyleneoxybenzoate, poly-1,3-propylene terephthalate, poly-1,6-hexylene terephthalate, and among these, polyethylene terephthalate, poly- 1,4-butylene terephthalate and polyethylene-2,6-nanophthalate are preferred. A crystalline polyester resin may be used individually by 1 type, and may use 2 or more types together.

  In addition, various additives, such as an impact strength modifier, a stabilizer, a lubricant, a filler, a pigment, a foaming agent, and an ultraviolet stabilizer, can be added to these resins as necessary.

  The blending ratio of the resin modifier of the present invention to the resin is preferably 1 to 40 parts, more preferably 1 to 30 parts, relative to 100 parts of the resin. If the amount is less than 1 part, the intended performance tends not to be obtained, and if it exceeds 40 parts, the possibility of bleeding out due to long-term storage or the like increases.

In the present specification, the term “parts” simply means “parts by weight”.
In this specification, the “average degree of substitution” is a value determined by proton nuclear magnetic resonance ( ¹ H-NMR).

  The present invention will be described in detail based on examples, but the present invention is not limited to these examples.

1. Synthesis Example 1
<Maltitol benzoate (average substitution degree 6.5)>
In a five-necked flask equipped with a stir bar, thermometer, cooling condenser, dropping funnel, and pH electrode connected to a pH meter, 30.0 parts of maltitol and 70.0 parts of water were charged and dissolved, and then dissolved in a water bath. While cooling to below ℃, 100 parts of cyclohexanone containing 79.0 parts of benzoyl chloride was gradually added and dissolved uniformly. While maintaining the temperature at 20 ° C. or lower, 50.1 parts of a 48% sodium hydroxide aqueous solution was added at a rate such that the pH was maintained at 10 to 11 from the dropping funnel. The dropping was completed within 1 hour. Thereafter, the water bath was removed, and stirring was continued for 1 hour at room temperature of 20 to 30 ° C. to complete the reaction. Thereafter, a slight amount of sodium carbonate was added and heated to convert benzoyl chloride remaining in a trace amount into sodium benzoate. And the maltitol benzoate was obtained by removing a solvent with a rotary evaporator. When the average degree of substitution was determined by ¹ H-NMR, it was 6.5.

Example 2
<Maltitol benzoate (average substitution degree 3.2)>
A maltitol benzoate was obtained in the same manner as in Example 1 except that 30.0 parts of maltitol and 39.0 parts of benzoyl chloride were used. The average degree of substitution was determined by ¹ H-NMR to be 3.2.

Example 3
<Sucrose toluic acid ester (average substitution degree 6.3)>
A sucrose toluic acid ester was obtained in the same manner as in Example 1 except that 30.0 parts of sucrose and 85.3 parts of toluic acid chloride were used instead of maltitol. The average degree of substitution determined by ¹ H-NMR was 6.3.

Example 4
<Sucrose toluic acid ester (average substitution degree 4.7)>
A sucrose toluic acid ester was obtained in the same manner as in Example 1, except that 30.0 parts of sucrose and 63.6 parts of toluic acid chloride were used instead of maltitol. The average degree of substitution determined by ¹ H-NMR was 4.7.

Example 5
<Maltitol toluic acid ester (average substitution degree 7.6)>
Maltitol toluic acid ester was obtained in the same manner as in Example 1 except that 30.0 parts of maltitol and 102.3 parts of toluic acid chloride were used in place of benzoyl chloride. The average substitution degree determined by ¹ H-NMR was 7.6.

Comparative Example 1
<Sucrose benzoate (average substitution degree 7.3)>
A sucrose benzoate was obtained in the same manner as in Example 1 except that 30.0 parts of sucrose and 89.9 parts of benzoyl chloride were used. The average degree of substitution determined by ¹ H-NMR was 7.3.

Comparative Example 2
<Sucrose benzoate (average substitution degree 6.0)>
A sucrose benzoate was obtained in the same manner as in Example 1 except that 30.0 parts of sucrose and 73.9 parts of benzoyl chloride were used. The average degree of substitution determined by ¹ H-NMR was 6.0.

Comparative Example 3
<Sucrose benzoate (average substitution degree 4.8)>
A sucrose benzoate was obtained in the same manner as in Example 1 except that 30.0 parts of sucrose and 59.1 parts of benzoyl chloride were used. The average degree of substitution determined by ¹ H-NMR was 4.8.

2. Evaluation <Hue>
5 g of each ester obtained in the above Examples and Comparative Examples was put in a test tube and heated in an oil bath at 130 ° C. for 15 hours. The hue of each sample before and after heating was determined according to the method described in JIS K2421. That is, each sample was diluted to 50% with toluene, and the numerical value of the APHA standard solution (Hazen color number: APHA) that was judged to be the same when the hue of the diluted solution was compared with the naked eye was recorded.

  The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 5 of the present invention, even after heating at 130 ° C. for 15 hours, no change was seen in the hue (APHA), indicating high thermal stability. This was the same in Example 2 and Example 4 with a relatively low average degree of substitution. On the other hand, in Comparative Examples 1 to 3, a large change in hue was observed before and after heating, and a tendency for the change to increase as the average substitution degree decreased was observed.

  The resin modifier of the present invention is excellent in phase solubility with an amorphous resin or a crystalline resin, and can improve molding processability, physical properties, flexibility, impact resistance, etc. Since it has the outstanding feature that coloring can be suppressed, it is useful as a modifier for resins, particularly resins that require optical transparency.

Claims (2)

Maltitol and general formula (I)

(In the formula, R ^{1 to} R ⁵ are groups independently selected from a hydrogen atom, an alkyl group, and an alkoxy group .)
An ester with an aromatic monocarboxylic acid represented by
The resin modifier whose average ester substitution degree of the said ester is 2.5-7.9. The average ester substitution degree resin modifier comprising 2.5 to 7.9 der luma Ruchitoru benzoic acid ester and / or maltitol tolyl ester.