TW201702299A - Ether bond-containing sulfur compound and resin composition - Google Patents

Abstract

To provide a sulfur compound which has an unprecedented novel structure, while exhibiting excellent water resistance and heat resistance. Also, to provide a resin composition which uses this sulfur compound. An ether bond-containing sulfur compound which has two or more mercapto groups and an ether bond; and a resin composition which contains this ether bond-containing sulfur compound and a curable resin.

Description

Sulfur compound containing ether bond and resin composition

The present invention relates to a sulfur compound and a resin composition containing an ether bond.

A sulfur compound having a mercapto group (SH) in a molecule is widely used in various fields by utilizing the reactivity of a mercapto group. There are many types of sulfur compounds in the past, and the applicant has provided various sulfur compounds having an ester bond (see Non-Patent Document 1).

Non-Patent Document 1: "thiocarboxylic acids", SC Organic Chemical Co., Ltd., [online], searched on March 19, 2015, Internet <URL: http://www.sco-sakai- Chem.com/products/products2_01.html>

As noted above, a variety of sulfur compounds have been present, and applicants have also provided various sulfur compounds having ester linkages. However, there is room for the development of sulfur compounds for new structures from the standpoint of expanding the range of choices for the best sulfur compounds in various applications. For example, previous sulfur compounds having an ester bond are very useful in various applications, but development of water resistance or heat resistance and reactivity have been developed. A space that is superior to the sulfur compounds that are more useful in various applications.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a sulfur compound which has an unprecedented new structure and is excellent in water resistance, heat resistance, reactivity, and the like. Further, it is also an object of the invention to provide a resin composition using such a sulfur compound.

The present inventors conducted various studies on novel sulfur compounds, and as a result, a novel sulfur compound having two or more mercapto groups and ether bonds and having a specific structural formula was successfully produced. This compound has high reactivity and is excellent in heat resistance, and is superior in water resistance to ether bonds as compared with the conventional sulfur compound having an ester bond. Further, it has been found that the resin composition containing the sulfur compound and the resin component is excellent in water resistance, heat resistance, reactivity, flexibility, and alkali resistance, and can also achieve low viscosity. As described above, it is thought that the above problems can be solved, and the present invention has been completed.

Further, in terms of technical common sense, the ester compound and the ether compound are not only greatly different in function or characteristics, but also difficult to substitute an ester bond with an ether bond.

That is, the present invention is a sulfur compound containing an ether bond represented by the following formula (1).

In the formula, A represents a residue of a polyol having two or more hydroxyl groups at the terminal, and an oxygen atom derived from the terminal hydroxyl group is bonded to n R ¹ and m R ² . R ^{1 is the} same or different and represents an alkylene group having 1 to 10 carbon atoms. R ^{2 is the} same or different and represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n is an integer of 2 or more, m is an integer of 0 or more, and the sum (n+m) corresponds to the total number of terminal hydroxyl groups which the polyol has.

The above polyol preferably has 2 to 6 terminal hydroxyl groups. The sulfur compound containing an ether bond in such a form is preferred because it has high reactivity and excellent usability.

Moreover, the present invention is also a resin composition containing the above-described sulfur compound containing an ether bond and a curable resin.

The sulfur compound containing an ether bond of the present invention is an unprecedented novel compound and is excellent in water resistance and heat resistance. The resin composition containing the compound and the curable resin is excellent not only in water resistance and heat resistance, but also excellent in reactivity, flexibility, and alkali resistance, and can achieve low viscosity, so that it can be used, for example, in the field of electrical-electronics, civil engineering, and construction. , coatings, optical fields and other fields.

Figure 1 is the TG and DTA analysis data for each of the products obtained in Examples 1 and 2.

2 is a TG and DTA analysis data of the compositions obtained in Examples 3 and 4, Comparative Examples 1, 2, and Reference Examples.

Fig. 3 is a photograph of the appearance obtained when the composition obtained in Example 4 was subjected to a boiling water absorption test. (a) is the appearance before boiling, and (b) is the appearance after boiling.

Fig. 4 is a photograph obtained by photographing the appearance of the composition obtained in Comparative Example 2 in a boiling water absorption test. (a) is the appearance before boiling, and (b) is the appearance after boiling.

[Sulfur compound containing ether bond]

The sulfur compound containing an ether bond of the present invention is represented by the above formula (1).

In the above formula (1), A represents a residue of a polyol having two or more hydroxyl groups at the terminal. The "residue of a polyol" means a structure obtained by removing a hydrogen atom (H) constituting a terminal hydroxyl group (OH) from a polyol, and an oxygen atom bonded to the hydrogen atom, that is, an oxygen atom derived from a terminal hydroxyl group and n R ¹ and m R ² bonds.

The polyhydric alcohol is not particularly limited as long as it is a compound having two or more terminal hydroxyl groups in one molecule. For example, an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol, a polyhydric alcohol containing an aromatic ring, a saccharide, its derivative, etc. are mentioned. Among them, aliphatic polyols, alicyclic polyols, and/or polyols containing an aromatic ring are preferred. More preferably, it is an aliphatic polyol.

The aliphatic polyol is preferably a carbon number of 2 to 30. Specific examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, and the like. Alkylene glycol; diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and other polyalkylene glycol; (poly) glycerol, trimethylolpropane, neopentyl a trihydric or higher polyhydric alcohol such as an alcohol, dipentaerythritol, sorbitol or sorbitol; or an alkylene oxide adduct (for example, an addition molar number of 1 to 50) ).

As the alicyclic polyol, for example, those having a carbon number of 3 to 30 are preferable. Specific examples thereof include alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

The polyhydric alcohol containing an aromatic ring is preferably a carbon number of 6 to 30. Specific examples thereof include bisphenol-based alkylene oxide adducts such as bisphenol A, bisphenol F, and bisphenol S (for example, Adding moles 2 to 30) and so on.

The terminal hydroxyl group of the above polyol may be two or more, more preferably 2 to 10, still more preferably 2 to 8, and particularly preferably 2 to 6. Thereby, it is a sulfur compound containing an ether bond which is more reactive and excellent in usability. The best is 3 to 6, which is a ternary to six-membered polyol.

In the above formula (1), R ^{1 is the} same or different and represents an alkylene group having 1 to 10 carbon atoms. The alkyl group may be linear or branched.

The number of carbon atoms of the alkylene group represented by the above R ¹ may be appropriately set according to the physical properties required for the sulfur compound containing an ether bond. For example, in applications requiring flexibility, the larger the carbon number, the better, and in applications requiring a high refractive index, the smaller the carbon number, the better. Specifically, for example, the carbon number of the alkylene group is preferably from 2 to 8, more preferably from 2 to 5. Further, in the case where a sulfur compound containing an ether bond is produced by the following preferred production method, R ¹ is derived from the structure of a halogenated olefin.

In the alkylene group represented by the above R ¹ , the carbon atom bonded to the sulfhydryl group may be a primary carbon atom, a secondary carbon atom, or a tertiary carbon atom. It is preferably a primary carbon atom or a secondary carbon atom. In the case of a secondary carbon atom, the sulfur compound containing an ether bond becomes a secondary mercaptan, and in this case, the hardening rate is suppressed, so when it is used for a resin composition containing a curable resin, the resin composition The single liquid stability of the material is excellent.

Further, the above R ¹ may have one or two or more substituents. The substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amine group, and a phosphoric acid group. Further, it is also preferred that R ¹ does not contain a substituent.

In the above formula (1), R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear or branched. Further, in the case of having two or more R ² , the R ² may be the same or different.

In the case where R ² represents an alkyl group, the carbon number thereof may be appropriately set according to the physical properties required for the sulfur compound containing an ether bond. For example, it is preferably 1 to 8, more preferably 1 to 5. As R ² , a hydrogen atom is particularly preferred.

Further, the above R ² may have one or two or more substituents. The substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amine group, and a phosphoric acid group. Further, it is also preferred that R ² does not contain a substituent.

In the above formula (1), n represents the number of structures represented by (R ¹ -SH), and is an integer of 2 or more. m represents the number of R ² and is an integer of 0 or more. The sum (n+m) of these is the total number of terminal hydroxyl groups which the polyol of the above A has. Preferably, n and m satisfy n≧m, and more preferably satisfy n>m. Further, m is preferably 2 or less, more preferably 1 or 0.

The sum of n and m (n+m) is, for example, 3 when the polyol to which A is added is trimethylolpropane, and 4 when the polyol to which A is added is neopentyl alcohol. When the polyol is di-trimethylolpropane, it is 4, and in the case where the polyol given A is dipentaerythritol, it is 6, which is for reference only.

The molecular weight of the above-mentioned sulfur compound-containing sulfur compound is, in terms of atomic weight (the mass of the carbon atom is 12.01), preferably 50 to 700. If it is 700 or less, it is advantageous from the viewpoint of reducing the viscosity. More preferably, it is 100 to 500, and further preferably 150 to 400.

The SH value of the above sulfur compound-containing sulfur compound is preferably from 5 to 50%. More preferably 10 to 35%.

In the present specification, the SH valence can be, for example, dissolved in a suitable organic solvent, using an electric potential difference auto-titration device (manufactured by Kyoto Electronics Manufacturing Co., Ltd., AT-610), by using oxygen in an iodine solution. The measurement was carried out by a reduction titration method.

The specific gravity of the above-mentioned sulfur compound-containing sulfur compound is, for example, a specific gravity of 25 ° C, for example, preferably 1.0 to 1.5. More preferably 1.05~1.3.

In the present specification, the specific gravity can be determined, for example, by measurement at 25 ° C by a hydrometer method.

The refractive index of the above-mentioned sulfur compound-containing sulfur compound is, for example, from 1.1 to 1.7, based on the refractive index at 25 °C. More preferably 1.3 to 1.6.

In the present specification, the refractive index can be determined, for example, by measuring a refractive index at a temperature of 25 ° C and a wavelength of 589 nm using a refractometer (manufactured by Atago Co., Ltd., DR-A1).

The viscosity of the above sulfur compound containing an ether bond is at a viscosity of 25 ° C, for example, preferably 1 to 10000 mPa. s. More preferably 1~3000mPa. s, further preferably from 1 to 500 mPa. s, especially good for 200mPa. Below s, the best is 120mPa. s below. Thus, the ether bond-containing sulfur compound of the present invention has a lower viscosity than the conventional sulfur compound, and thus can be preferably used for applications requiring low viscosity.

In the present specification, the viscosity can be determined, for example, by measuring at 25 ° C using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVB-10H).

[Manufacturing method of sulfur compound containing ether bond]

The sulfur bond-containing sulfur compound of the present invention can be produced, for example, by reacting a polyhydric alcohol with a halogenated olefin to etherify two or more terminal hydroxyl groups (referred to as reaction 1), and reacting it with a sulfuric acid. The reaction (referred to as Reaction 2) is further supplied to the alkali hydrolysis and neutralization reaction. Further, if necessary, after the reaction 1 or the reaction 2, the residual terminal hydroxyl group may be alkoxylated, or after the alkali hydrolysis and the neutralization reaction, a purification step (filtration or the like) may be carried out.

The above reaction 1 is a reaction of a polyol with a halogenated olefin. The reaction conditions are not special The limit is set to the usual general condition. One type or two or more types of each material can be used.

The polyhydric alcohol may, for example, be the above compound.

The halogenated olefin is preferably an olefin having 1 to 10 carbon atoms and having a halogen atom, and is derived from the structure to form R ¹ in the above formula (1). The halogen atom is not particularly limited, and is preferably a chlorine atom from the viewpoint of availability, cost, reactivity, and the like. The carbon number of the olefin may be appropriately set according to the physical properties required for the sulfur compound containing an ether bond as a target. For example, it is preferably 2 to 8, more preferably 2 to 5. As the halogenated olefin, an allyl chloride is particularly preferred.

In the above-mentioned reaction 1, the ratio of use of the polyol to the halogenated olefin may be appropriately set according to the structure, required physical properties, production efficiency, and the like of the sulfur compound containing the ether bond as the target. For example, it is preferable to set the halogenated olefin to 2 mol or more, and preferably 20 mol or less, to 1 mol of the terminal hydroxyl group which the polyol has.

The above reaction 2 is a reaction of an ether compound formed in the reaction 1 with a sulfuric acid. The reaction conditions are not particularly limited, and from the viewpoint of improving the reaction efficiency, the reaction temperature is preferably 30 to 80 °C. One type or two or more types of each material can be used.

The thiocarboxylic acid is not particularly limited as long as it has a structure represented by -C=O-SH, and is preferably a compound represented by the following formula (2).

In the formula, R ³ represents a hydrocarbon group, a hydroxyl group, a halogen atom or a hydrogen atom. The hydrocarbon group is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. The carbon number is preferably from 1 to 30, more preferably from 1 to 18. Among them, an alkyl group is preferred.

Specific examples of the sulfur carboxylic acid include sulfuric acid, propanethioic acid, and thiobenzoic acid. Among them, sulfuric acid and/or thiobenzoic acid are preferably used from the viewpoint of availability or cost.

In the above-mentioned reaction 2, the ratio of use of the ether compound to the sulfuric acid produced in the reaction 1 may be appropriately set depending on the structure, required physical properties, production efficiency, and the like of the sulfur compound containing the ether bond as the target. For example, it is preferred to set the thiocarboxylic acid to 2 mol or more, and preferably 20 mol or less, based on 1 mol of the ether bond of the ether compound formed in the reaction 1.

In the above production method, hydrolysis is carried out using a base after the reaction 2, and further neutralization is carried out. The base is not particularly limited, and one or two or more kinds of bases which are usually used can be used. In the alkali hydrolysis step, from the viewpoint of improving the efficiency of the hydrolysis reaction, the temperature is preferably set to 30 to 80 °C. Further, in the neutralization step, one or two or more kinds of commonly used acids may be used.

[use]

The sulfur bond-containing sulfur compound of the present invention has high reactivity and is excellent in water resistance and heat resistance, and thus is, for example, a curing agent (preferably an epoxy resin curing agent); and is obtained by using active rays such as ultraviolet rays, electron beams, and X-rays. Hardening monomer; main component of urethane resin; chain transfer agent of monomer having double bond in the molecule such as acrylic acid; various rubber vulcanizing agents and crosslinking agents; various synthetic raw materials; reducing agent, etc. In the electrical and electronic fields, civil engineering - construction, coatings, optical and other fields.

Specifically, for example, it can be preferably used for: an electronic device adhesive (underfill, a camera module adhesive, an optical read head adhesive, etc.), an LED sealant, a semiconductor sealant, a solder resist (solder) Resist), printed circuit board material, conductive paste material, color filter Protective coating (overcoat), coil impregnating adhesive, anisotropic conductive film material, cutting temporary fixing adhesive and other electrical-electronic parts materials; bridge seismic strengthening, concrete reinforcement, building flooring, water and sewage facilities Lining, drainage-permeable paving, vehicle-aircraft adhesives, composite materials for sporting goods such as golf clubs or tennis rackets, adhesives for tile attaching adhesives, asphalt modifiers, etc.; marine coatings Coatings for inner surfaces of beverage cans, coatings for anti-corrosion coatings, coatings for flooring, primers for automotive use, other industrial electrodeposition coatings, pipe interior and exterior coating, various roads Coating materials such as paints (surface paints, landscape paints, etc.). In such applications, the above-mentioned sulfur compound containing an ether bond is preferably used as a curing agent (preferably an epoxy resin hardener).

Further, for example, it can be preferably used for a film material (an antireflection film, a wide viewing angle film, a polarizing film, a diffusion film, a film material for a flat panel display such as a ruthenium film, etc.), a coating material (various films or resins, metals, shells). Body, decorative board, beverage can, etc.), UV-curable adhesive (optical adhesive such as optical lens, optical fiber, or optical path bonding, DVD or optical disk bonding adhesive, optical read head adhesive, etc.), UV-curable ink , photosensitive solder resist, photo-curing adhesive, color resist, black matrix, photo spacer, various sealants (liquid crystal sealant, etc.), optically transparent resin material (OCR) , light-forming materials, dental materials, polymer battery materials, printing plate materials, manicure, potting ink, optical waveguides, and the like. In such applications, the above-mentioned sulfur compound containing an ether bond is preferably used as the hardening monomer.

Further, for example, it may be preferably used for a plastic lens or an interlayer insulating film. In this application, the above-mentioned sulfur compound containing an ether bond is preferably used as a main component of the amine resin. Further, it is preferably used for an optical transparent sheet (OCA), an acrylic tape, a wallpaper ink or the like, and is preferably used as a chain transfer agent in such applications.

Further, by using the sulfur compound containing an ether bond of the present invention in combination with a sulfur compound containing an ester group, a cured product exhibiting an arbitrary bending modulus can be provided. The sulfur compound containing an ester group is preferably a compound having a mercapto group or an ester bond, and is preferably a sulfur carboxylic acid described in Non-Patent Document 1. Thus, the composition containing the "sulfur compound containing an ether bond of the present invention" and the "sulfur compound containing an ester group" is included in the preferred embodiment of the present invention. The mass ratio (sulfur compound containing an ether bond/sulfur compound containing an ester group) in this case is not particularly limited, and is preferably, for example, 1 to 99/99 to 1.

[Resin composition]

The resin composition of the present invention contains the above-described sulfur compound containing an ether bond of the present invention and a curable resin. Each of the components may be used alone or in combination of two or more.

In addition, the curable resin is not particularly limited as long as it is a curable compound, and may be a monomer, an oligomer, a polymer, or a mixture thereof.

The curable resin is not particularly limited, and any of a thermosetting resin and a thermoplastic resin can be preferably used. Preferably, it has a group selected from the group consisting of an epoxy group, a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group, an allyl ether group, and an isocyanate group (-N=C=O). At least one base compound. These compounds are preferred because of their high reactivity. The curable resin is more preferably an epoxy resin (preferably bisphenol A epoxy resin), an amine resin resin (preferably hexamethylene diisocyanate), or a polyene compound (preferably pentaerythritol III). Allyl ether), acrylic resin.

In the resin composition, the content ratio of the sulfur compound containing an ether bond to the curable resin is not particularly limited. For example, a curable resin/sulfur compound containing an ether bond (weight ratio) is preferably 100/0.01 to 500. Among them, it is preferably from 100/0.01 to 300. More preferably 100/0.01 ~200. For example, in the case where an epoxy resin is used as the curable resin, it is further preferably from 100/1 to 150, particularly preferably from 100/1 to 100, and further preferably, in the case of using an amine resin, 100/ 1 to 200, particularly preferably 100/1 to 150, and in the case of using a polyene compound, it is further preferably 100/0.01 to 300, and particularly preferably 100/0.01 to 200.

Hereinafter, preferred specific examples of the curable resin will be described.

- epoxy resin -

The epoxy resin is not particularly limited, and is preferably a compound obtained by condensation of epichlorohydrin with a polyhydric phenol or a polyhydric alcohol such as a bisphenol. Specific examples thereof include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, and anthraquinone type. A novolac type epoxy resin such as a novolac type, a phenol novolac type, an o-cresol novolac type, a tris(hydroxyphenyl)methane type or a tetraphenylol ethane type. Further, a glycidyl ester type epoxy resin obtained by condensation of epichlorohydrin with a phthalic acid derivative or a carboxylic acid such as a fatty acid; by epichlorohydrin with an amine or a cyanuric acid; Epoxypropylamine type epoxy resin obtained by the reaction of carbendazole, and epoxy resin modified by various methods. Among them, a epoxy propyl ether type epoxy resin is preferable, and as described above, a bisphenol A type epoxy resin is more preferable. Further, a compound having an epoxy group and an acrylate group or a methacrylate group (generally referred to as "(meth) acrylate group") is also preferred.

-amine resin -

The amine resin is not particularly limited, and for example, a compound obtained by a reaction of an isocyanate compound and a polyol compound is preferred. Further, the reaction product of the ether bond-containing sulfur compound and the isocyanate compound in the present invention is also preferable, and the reaction product is contained in the "resin composition containing a sulfur compound containing an ether bond and a curable resin" as referred to in the present invention.

The isocyanate compound is not particularly limited, and examples thereof include toluene diisocyanate (TDI), diphenylmethane diisocyanate, xylylene diisocyanate, stilbene diisocyanate, and phenylene diene. Isocyanate, m-tetramethyl-decyl diisocyanate, methylcyclohexane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, norbornene Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Diisocyanate and the like. Among them, as described above, hexamethylene diisocyanate is preferred.

-polyene compounds -

The polyene compound is preferably a compound having an unsaturated group such as a vinyl group, a vinyl ether group, an acrylate group, a methacrylate group or an allyl ether group. Examples of the compound having a vinyl group include vinyl decane, ethylene, propylene, and the like.

Examples of the compound having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene glycol divinyl ether. Ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, neopentyl Tetraol type tetravinyl ether and the like.

Examples of the compound having an acrylate group include lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, caprolactone modified tetrahydrofurfuryl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, and acrylic acid. Oxime ester, benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxytetraethylene glycol acrylate, decyl phenoxy acrylate, decyl benzene Oxytetraethylene glycol acrylate, methoxy diethylene glycol Acrylate, ethoxy diethylene glycol acrylate, butoxyethyl acrylate, butoxy triethylene glycol acrylate, 2-ethylhexyl polyethylene glycol acrylate, nonyl phenyl polypropylene glycol acrylate Methoxydipropylene glycol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycerin acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, and the like.

Examples of the compound having a methacrylate group include lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, caprolactone modified tetrahydrofurfuryl methacrylate, and methyl group. Cyclohexyl acrylate, dicyclopentanyl methacrylate, isodecyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, phenoxy diethylene glycol methacrylate Ester, phenoxytetraethylene glycol methacrylate, nonylphenoxyethyl methacrylate, nonylphenoxytetraethylene glycol methacrylate, methoxydiethylene glycol methacrylate , ethoxy diethylene glycol methacrylate, butoxyethyl methacrylate, butoxy triethylene glycol methacrylate, 2-ethylhexyl polyethylene glycol methacrylate, fluorenyl Phenyl polypropylene glycol methacrylate, methoxy dipropylene glycol methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid Glyceride, polyethylene glycol methacrylate, polypropylene glycol methyl Acid esters.

Examples of the compound having an allyl ether group include trimethylolpropane diallyl ether and pentaerythritol triallyl ether.

Among the above polyene compounds, a compound having an allyl ether group is preferred. As described above, pentaerythritol triallyl ether is more preferred.

-Acrylic-

The acrylic resin is not particularly limited, and for example, a (meth)acrylic monomer or (A) In addition to the acrylic oligomer, a polymer or a copolymer containing at least one of these may be mentioned.

In addition, the resin composition may contain one or two or more kinds of components other than the sulfur compound containing an ether bond and a curable resin (referred to as "other components").

The other components are not particularly limited, and examples thereof include a polymerization initiator (for example, an alkylbenzophenone-based photopolymerization initiator such as α-hydroxyalkylphenone) and a curing catalyst. (for example, an amine compound such as tri-ethyltetramine), a curing agent (for example, an acid anhydride such as methylhexahydrophthalic anhydride), a curing accelerator (for example, an organic phosphate such as acid butyl phosphate), or the like.

The content of the other components is not particularly limited, and may be appropriately set according to the use or function of the other components. For example, it is preferably 30% by weight or less based on 100% by weight of the resin composition.

The viscosity of the resin composition is not particularly limited, and can be appropriately set depending on the use, etc., and the use of the sulfur compound containing an ether bond of the present invention can also achieve low viscosity.

As a particularly preferable embodiment of the resin composition of the present invention, the following forms 1) to 4) can be mentioned.

1) A resin composition containing the sulfur compound containing a ether bond, a polyene compound, and a polymerization initiator of the present invention. The blending quality of the three components is preferably from 0.01 to 300 parts by weight (preferably from 0.01 to 200 parts by weight) based on 100 parts by weight of the polyene compound, and the polymerization initiator is 0.1~. 10 parts by weight (preferably 0.3 to 1 part by weight).

2) A resin composition containing the sulfur compound containing an ether bond, an epoxy resin, and a curing catalyst of the present invention. The blending quality of the three components is preferably relative to the weight of the epoxy resin 100 The sulfur compound containing an ether bond is 1 to 150 parts by weight (preferably 1 to 100 parts by weight), and the polymerization initiator is 0.1 to 10 parts by weight (preferably 0.3 to 1 part by weight).

3) A resin composition containing the sulfur compound containing an ether bond, an epoxy resin, and an acid anhydride of the present invention. The blending quality of the three components is preferably from 1 to 150 parts by weight (preferably from 1 to 100 parts by weight) based on 100 parts by weight of the epoxy resin, and from 10 to 100 parts by weight of the acid anhydride. (preferably 30 to 70 parts by weight).

4) A resin composition containing the sulfur compound containing an ether bond, an amine resin, and a hardening accelerator of the present invention. The blending quality of the three components is preferably from 1 to 200 parts by weight (preferably from 1 to 150 parts by weight) based on 100 parts by weight of the amine resin, and from 0.1 to 10, and the hardening accelerator is from 0.1 to 10 parts by weight. Parts by weight (preferably 1 to 5 parts by weight).

[Examples]

In order to explain the present invention in detail, the following examples are given, but the invention is not limited to the embodiments. "%" means "% by weight (% by mass)" unless otherwise stated.

<Analysis and evaluation method of physical properties>

1. Analysis of sulfur compounds containing ether linkages

In the following examples, ¹ H-NMR and TG-DTA were analyzed by the following methods. Analysis of other physical properties and the like is carried out by the above method.

(1) ¹ H-NMR

The sample was dissolved in chloroform and measured by a nuclear magnetic resonance apparatus (manufactured by Bruker BioSpin, AVANCE III, 400 MHz).

(2) TG-DTA (thermogravimetry - differential heat)

The measurement was carried out by using a thermogravimetric-differential thermal analyzer (manufactured by SII NanoTechnology Co., Ltd., TG/DTA6300) under a temperature rise condition of 10 ° C/min.

2. Physical property evaluation of resin composition

(1) Viscosity

The epoxy resin blend was placed in a 100 mL glass vial and adjusted to 25 ° C using a thermostat. The viscosity measurement was performed using a B-type viscometer TVB-10H (manufactured by Toki Sangyo Co., Ltd.) under the following conditions. The results are shown in Table 1.

Rotor: No.3

Measurement time: 1 minute

Rotation speed: viscosity 2000 (mPa.s) or less, 50 rpm; viscosity 5000 (mPa.s) or less, 20 rpm; viscosity 5000 (mPa.s) or more, 10 rpm

(2) DSC (differential scanning heat)

About 2 mg of the epoxy resin blend was taken and measured using a differential scanning calorimeter (manufactured by Rigaku Co., Ltd., Thermo plus EVO DSC 8230) from room temperature to 250 ° C at a temperature rising rate of 10 ° C / min. The heat generation onset temperature (°C) is shown in Table 1.

(3) TG-DTA (thermogravimetry - differential heat)

The measurement was carried out under a nitrogen atmosphere at a temperature rise condition of 10 ° C/min using a thermogravimetric-differential thermal analysis apparatus (manufactured by Seiko Instruments Inc., TG/DTA6300). This is shown in Figure 2.

(4) TMA (thermomechanical analysis)

Using a thermomechanical analysis device (manufactured by Rigaku Corporation, Thermo plus EVO TMA 8310), The cured epoxy resin (width: 3 mm × length: 15 mm × thickness: 3 mm) was measured under a nitrogen atmosphere at a temperature rising rate of 2 ° C / min. Tg is shown in Table 1.

(5) Thermal expansion rate

The length of the cured test piece (width 10 mm × length 30 mm × thickness 3 mm) at room temperature was measured with a micrometer. Then, the test piece was placed in a dryer set to 105 ° C, and the length was measured again after 1 hour. Furthermore, the test is based on JIS K6911 (2006). This is shown in Table 1.

(6) bending modulus

A three-point bending test was performed on a cured epoxy resin (width: 10 mm × length: 60 mm × thickness: 3 mm) at a load speed of 1.5 mm/min using a desktop precision universal testing machine (Autograph AGS-X, manufactured by Shimadzu Corporation). This is shown in Table 1.

(7) boiling water absorption rate

The cured epoxy resin (20 mm in diameter × 1 mm in thickness) was dried for 2 hours using a dryer set at 60 °C. The treated test piece was cooled to room temperature in a desiccator and accurately weighed. Then, 60 mL of distilled water and a test piece were placed in a beaker and boiled for 6 hours. Thereafter, it was cooled by running water for 30 minutes, and after wiping the surface, it was placed in a weighing bottle within 1 minute, and the mass after water absorption was accurately weighed. The weight change rate (mass change rate) (%) is shown in Table 1. Further, the appearance of the test piece after the end of the test was observed (the appearance photographs before and after boiling of Example 4 and Comparative Example 2 are shown in Figs. 3 and 4). Furthermore, the test is based on JIS K6911 (2006).

(8) Alkali resistance test

The cured epoxy resin (width 10 mm × length 30 mm × thickness 3 mm) was dried for 2 hours using a dryer set at 60 °C. The treated test piece was cooled to room temperature in a desiccator and accurately weighed. Then, immersed in a 30 mL spiral tube containing 5% sodium hydroxide aqueous solution, 20 mL, Keep it at 25 ° C for 7 days. The container was shaken calmly every 24 hours to mix the test solution. After the test time, it was quickly washed with distilled water, and the surface was wiped, and then placed in a weighing bottle within 1 minute to accurately weigh the mass after the test. The weight change rate (mass change rate) (%) is shown in Table 1. Furthermore, the test is based on JIS K6911 (2006).

<Production of sulfur compound containing ether bond>

Example 1 (TMPT) Trimethylolpropane diallyl ether (350 g, 1.63 mol) was added to a round bottom flask and then heated to 40 °C. After adding sulfuric acid (274 g, 3.59 mol) dropwise, the mixture was stirred at 40 ° C for 4 hours. After adding a 20% aqueous ammonia solution (500 g) to the reaction liquid, the mixture was stirred at 55 ° C for 15 hours. After the liquid separation, toluene (460 g) and a 5% aqueous sulfuric acid solution (315 g) were added to the organic layer. After the liquid separation, water (315 g) was added to the organic layer. The organic layer was separated and dried, and trimethylolpropane dipropane thiol (440 g, yield 95%) (referred to as TMPT) was obtained as a colorless transparent oil. The NMR analysis results are shown below, and the TG-DTA analysis results are shown in Fig. 1 .

¹ H-NMR (400MHz, CDCl ₃ ): δ 0.82 (t, 3H), δ 1.31-1.37 (m, 4H), δ 1.82-1.88 (m, 4H), δ 2.57-2.63 (m, 4H), δ 2.82(br,1H),δ 3.35-3.42(m,4H),δ 3.50(t,4H),δ 3.56(s,2H)

From the results of the NMR analysis, it was confirmed that the product obtained in Example 1 is trimethylolpropane dipropanethiol (C ₁₂ H ₂₆ O ₃ S ₂ ) represented by the following formula (a).

The results of analysis of various physical properties of the TMPT obtained in Example 1 are shown in under.

Appearance: colorless transparent liquid

SH price: 21.7%

Specific gravity (25 ° C): 1.08

Refractive index (25 ° C): 1.50

Viscosity (25 ° C): 64 mPa. s

Example 1 '(TMPT)

After adding trimethylolpropane diallyl ether (350 g, 1.63 mol) to a round bottom flask, it was heated to 40 °C. After adding sulfuric acid (274 g, 3.59 mol) dropwise, the mixture was stirred at 40 ° C for 4 hours. After adding a 20% aqueous ammonia solution (500 g) to the reaction liquid, the mixture was stirred at 55 ° C for 15 hours. After liquid separation, a 5% aqueous solution of sulfuric acid (315 g) was added to the organic layer. After liquid separation, water (315 g) was added to the organic layer. The organic layer was separated and dried, and trimethylolpropane dipropanethiol (441 g, yield 95%) (referred to as TMPT) was obtained as a colorless transparent oil. This TMPT is a compound having the same physical properties and structure as the TMPT obtained in the above Example 1.

Example 2 (PEPT) After adding pentaerythritol triallyl ether (350 g, 1.37 mol) to a round bottom flask, it was heated to 40 °C. After adding sulfuric acid (343 g, 4.51 mol) dropwise, the mixture was stirred at 40 ° C for 4 hours. After adding a 20% aqueous ammonia solution (560 g) to the reaction liquid, the mixture was stirred at 55 ° C for 15 hours. After the liquid separation, toluene (490 g) and a 5% aqueous sulfuric acid solution (350 g) were added to the organic layer. After the liquid separation, water (350 g) was added to the organic layer. The organic layer was separated and concentrated to dryness, and neopentyl alcohol tripropane thiol (478 g, yield 98%) (referred to as PEPT) was obtained as a colorless, transparent oil. The NMR analysis results are shown below, and the TG-DTA analysis results are shown in Fig. 1 .

¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.35 (t, 3H), δ 1.80-1.86 (m, 6H), δ 2.55 - 2.61 (m, 6H), δ 2.79 (br, 1H), δ 3.40 ( s,6H),δ 3.48(t,6H),δ 3.65(s,2H)

From the results of the NMR analysis, it was confirmed that the product of Example 1 is neopentyl alcohol tripropane thiol (C ₁₄ H ₃₀ O ₄ S ₃ ) represented by the following formula (b).

The analysis results of various physical properties of the PEPT obtained in Example 2 are shown below.

Appearance: colorless transparent liquid

SH price: 26.6%

Specific gravity (25 ° C): 1.13

Refractive index (25 ° C): 1.52

Viscosity (25 ° C): 100mPa. s

Example 2' (PEPT) After adding pentaerythritol triallyl ether (350 g, 1.37 mol) to a round bottom flask, it was heated to 40 °C. After adding sulfuric acid (343 g, 4.51 mol) dropwise, the mixture was stirred at 40 ° C for 4 hours. After adding a 20% aqueous ammonia solution (560 g) to the reaction liquid, the mixture was stirred at 55 ° C for 15 hours. After liquid separation, a 5% aqueous solution of sulfuric acid (350 g) was added to the organic layer. After the liquid separation, water (350 g) was added to the organic layer. The organic layer was separated and concentrated to dryness, and fresh pentaerythritol tripropane thiol (479 g, yield 98%) (referred to as PEPT) was obtained as a colorless transparent oil. This PEPT is a compound having the same physical properties and structure as the PEPT obtained in the above Example 2.

As can be seen from Fig. 1, the heat resistance of TMPT and PEPT obtained in Examples 1 and 2 Excellent. Further, it is clear from the above structural formula that since it has an ether bond instead of an ester bond, the ether bond is not hydrolyzed as compared with the conventional sulfur compound having an ester bond, and therefore, water resistance is also excellent.

<Production of Resin Composition>

First, the following components were prepared as raw material components.

(A) component

. Bisphenol A type epoxy resin ("jER828", manufactured by Mitsubishi Chemical Corporation)

(B) component

. Trimethylolpropane dipropane thiol ("TMPT", compound obtained in Example 1)

. Neopentyl alcohol tripropane thiol ("PEPT", compound obtained in Example 2)

. 1,4-butanediol bis(3-mercaptopropionate) ("BDMP", manufactured by SC Organic Chemical Co., Ltd.)

. Trimethylolpropane tris(3-mercaptopropionate) ("TMMP", manufactured by SC Organic Chemical Co., Ltd.)

. Tris-isosuccinic acid tris[(3-decylpropenyloxy)ethyl]ester ("TEMPIC", manufactured by SC Organic Chemical Co., Ltd.)

(C) component

. Amine addition hardening accelerator ("Amicure PN-23", manufactured by Ajinomoto Fine-Techno)

. Anhydride-based hardener ("RIKACID MH-700", manufactured by Nippon Chemical and Chemical Co., Ltd.)

Examples 3 and 4, Comparative Examples 1 to 3, and Reference Examples

The component (A), the component (B), and the component (C) described in the weighing table 1 were placed in a disposable cup, and a self-rotating agitating defoamer manufactured by Shinky Co., Ltd. ("defoaming") was used. Kentaro ARE-310") was stirred for 5 minutes (referred to as "epoxy resin blend"). The obtained blend was cured at 80 ° C for 1 hour and at 120 ° C for 1 hour (referred to as "epoxy resin hard" Compound").

For each of the examples, the epoxy resin blend and the epoxy resin cured product were evaluated for physical properties by the above method. The results are shown in Table 1 and Figure 2.

According to the above results, the resin composition containing the ether bond-containing sulfur compound (Examples 3 and 4) in the present invention is excellent in workability and workability because of low resin viscosity, and has high reactivity at the initial temperature of heat generation. Low temperature hardening can be expected; since the thermal expansion rate is low, a cured product excellent in dimensional stability can be obtained; since the Tg based on TMA is low and the bending elastic modulus is also low, the flexibility is excellent; the alkali resistance is excellent; Since the transparency can be maintained (see FIGS. 3 and 4), the water resistance is excellent. Therefore, the resin composition containing the ether bond-containing sulfur compound of the present invention is suitable for various uses.

Claims (3)

A sulfur compound containing an ether bond, represented by the following formula (1), In the formula, A represents a residue of a polyol having two or more hydroxyl groups at the terminal, and an oxygen atom derived from the terminal hydroxyl group is bonded to n R ¹ and m R ² ; R ^{1 is the} same or different and represents a carbon number. 1 to 10 alkylene group; R ^{2 is the} same or different, and represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; n is an integer of 2 or more, and m is an integer of 0 or more, and the sum of n+m) corresponds to the total number of terminal hydroxyl groups of the polyol. The sulfur compound containing an ether bond according to the first aspect of the patent application, wherein the polyol has 2 to 6 terminal hydroxyl groups. A resin composition comprising a sulfur compound containing an ether bond and a curable resin according to claim 1 or 2.