JP5273904B2 - Additive for resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having a sulfur atom and a benzene ring skeleton and suitably usable for applications of an additive, etc., controlling the refractive index without deteriorating various characteristics such as thermal characteristics possessed by the resin such as a transparent resin and to provide an additive for the resin and a resin composition comprising the compound. <P>SOLUTION: The additive for the resin is composed of the compound having the sulfur atom and the benzene ring skeleton. The compound having the sulfur atom and the benzene ring skeleton is a compound having a thianaphthene skeleton and/or a phenyl disulfide skeleton in the molecule. The resin composition comprises the additive for the resin. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to a resin additive and a resin composition. More specifically, in addition to raw materials for various industrial products, compounds having a sulfur atom and a benzene ring skeleton that are being studied for various uses, and additives for resins containing such compounds and for the resins The present invention relates to a resin composition comprising an additive.

Additives for resins are widely used industrially in order to improve the properties of resins and to give them new properties. Among such additives for resins, in recent years, utilization in the field of optical materials is expected especially with the remarkable development of information-related technology. For example, it is used in the field of optical materials such as optical fibers, optical waveguides, optical recording disks, optical films, display substrates, etc., and is currently being tried to improve or improve various properties of transparent resins used in optical materials. There are many mistakes. In such a field, it is desired that the additive for resin is applied to the improvement of the optical properties of the resin, but at present, no satisfactory additive has been developed.

Regarding a conventional optical member, a polymerizable composition for an optical member containing a polymerizable monomer having a refractive index different from that of a compound having a sulfur atom (see, for example, Patent Document 1), at least constituting a transparent polymer resin matrix An optical member comprising one kind of polymer and at least one cyclic sulfide compound having a difference in solubility parameter and a difference in refractive index in comparison with the polymer, and having a distribution in the concentration of at least one kind of the compound ( For example, refer to Patent Document 2), and a plastic optical member (for example, refer to Patent Document 3) that includes a polymer as a matrix and a region having a refractive index distribution containing a halogenated thiophene compound is disclosed. However, in fields where development is strongly demanded, such as optical material applications, there is room for improvement as an additive for resin that can exhibit further sufficient performance.
JP2003-292541A (2nd page) JP 2003-344676 A (second page) JP 2004-264746 A (2nd page)

The present invention has been made in view of the above situation, and can be suitably used for applications such as additives that can control the refractive index without impairing various properties such as thermal properties of resins such as transparent resins. It is an object of the present invention to provide a compound having a sulfur atom and a benzene ring skeleton, and a resin additive and a resin composition containing such a compound.

As a result of various studies on the additive for resin, the present inventors have found that when a compound having a sulfur atom and a benzene ring is used, the compound exhibits a high refractive index and can be suitably applied to various applications. In addition, a resin additive containing a compound having a sulfur atom and a benzene ring skeleton has good physical properties as a resin additive such that it has good compatibility with the resin and does not impair the strength of the resin. It has been found that it has excellent functions such as the above, and has come up with the idea that the above problems can be solved brilliantly. Furthermore, it has been found that an additive for a resin containing such a compound exhibits excellent characteristics such as low optical transmission loss and bending loss, and high heat resistance. For example, optical fiber, optical waveguide, optical recording disk, optical It has also been found that the present invention can be suitably applied to optical materials such as films and display substrates, and the present invention has been achieved.

That is, the present invention is an additive for resin composed of a compound having a sulfur atom and a benzene ring skeleton,
The compound having a sulfur atom and a benzene ring skeleton is represented by the following formula (1);

A thianaphthene skeleton and / or the following formula (2):

The additive for resin which is a compound which has the phenyl disulfide frame | skeleton represented by these in a molecule | numerator.
The present invention is described in detail below.

The additive for resin of the present invention is composed of a compound having a sulfur atom and a benzene ring skeleton in the molecule (hereinafter also referred to as a sulfur-containing compound). A sulfur atom is an atom having excellent heat resistance and a high refractive index, and a rigid ring structure such as a benzene ring has a high refractive index and has a low loss of mechanical strength against the resin. The sulfur-containing compound having a structure, when used as an additive for a resin, can easily control the refractive index of the resin, does not impair the strength of the resin, and has various excellent properties such as good compatibility with the resin. Has characteristics. Therefore, the effect of controlling the refractive index can be sufficiently exhibited without impairing various characteristics such as thermal characteristics of the resin such as the transparent resin, and it can be suitably used for various applications.

The sulfur-containing compound is not particularly limited as long as it has a thianaphthene skeleton and / or a phenyl disulfide skeleton (hereinafter also simply referred to as a basic skeleton) in the molecule, but the following formula (1);

And / or the following formula (3):

It is preferable that it is diphenyl disulfide represented by these. Since these compounds have a small molecular weight, they can cause a significant change in refractive index when added in a small amount, and can be suitably used as an additive for resins. Further, it is a general-purpose product, is easily available, and is a stable compound that is not easily decomposed by UV irradiation or the like, and therefore has an advantage of excellent handling. It can also be used as a raw material for derivatives having various substituents shown below.

As the compound having the thianaphthene skeleton and / or phenyl disulfide skeleton in the molecule, derivatives having various substituents on the basic skeleton are preferable in addition to the thianaphthene and diphenyl disulfide.
The substituent is not particularly limited as long as it exhibits the effects of the present invention. (1) A halogen atom, a heteroatom, a deuterium atom, and a substituent having at least one atom among them, (2 ) Aromatic hydrocarbons, heterocyclic rings, and substituents having at least one of these atomic groups are preferred.

In the above (1), the halogen atom and the hetero atom have a high atomic refractive index, and the sulfur-containing compound having such an atom can be a compound having a high refractive index and a low molecular weight. Therefore, the additive for resin composed of the above sulfur-containing compound can be arbitrarily set the refractive index without impairing the transparency and mechanical properties of the resin with a small amount of addition, so the transmission loss is small and the refractive index difference Large additive for resin.
The additive for resin may absorb light to be transmitted due to stretching vibration due to the C—H bond contained in the additive. However, the C—H bond is changed to a C—D bond using a deuterium atom. Thus, such transmission loss can be reduced.

In the above (2), the aromatic hydrocarbon and the heterocyclic ring are atomic groups having a high refractive index, and the sulfur-containing compound having these atomic groups often has a high molecular weight and a high melting point. . The additive for resin composed of such a sulfur-containing compound is difficult to plasticize the resin, can be excellent in mechanical properties and heat resistance, and should be used suitably in various environments. It can be used as an additive for resin.

In the above substituent, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, as long as the compound after substitution can sufficiently exhibit the control of the refractive index.
As the halogen atom, a compound having a small atomic weight and a high atomic refractive index is preferred because the smaller the molecular weight of the compound after substitution, the smaller the added amount can exert the effect of controlling the refractive index. From the viewpoint of atomic refractive index, a chlorine atom, a bromine atom, and an iodine atom are preferable. In the present invention, since it has the basic skeleton as described above, even when it does not contain a fluorine atom, the effect of controlling the refractive index can be sufficiently exhibited.
From the viewpoint of atomic weight, a chlorine atom is preferable, and from the viewpoint of “atomic refractive index / atomic weight”, a bromine atom is preferable because the refractive index can be increased more efficiently. Therefore, when using a halogen atom as a substituent, it is preferable to select and use it suitably according to the compound obtained.

The halogen atom is represented by C _n H _{2n + 1-m} X _m (X represents a halogen atom. N and m are integers of 1 or more, and 2n + 1-m is an integer of 0 or more.) The halogen-substituted alkyl group may be contained in the sulfur-containing compound. As carbon number n of a halogen-substituted alkyl group, 1-20 are preferable and 1-15 are more preferable. The halogen number m of the halogen-substituted alkyl group can be appropriately selected from 1 to 2n + 1 integers depending on the number of carbon atoms and the halogen atom used. For example, when n = 1 and X = F, a form of m = 2n + 1 in which all hydrogen atoms of the alkyl group are substituted with halogen atoms is preferable. As the halogen-substituted alkyl group, a trifluoromethyl group is preferable.

As said hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are suitable. These atoms may be included in the sulfur-containing compound as a cyano group, a nitro group, an amino group, a carbonyl group, or the like, and are included in a ring structure such as a pyridine ring. Also good. Further, it may be contained in the form of an ether bond, an ester bond or the like. The amino group may be quaternized.

Examples of the aromatic hydrocarbon, heterocyclic ring, and other rings include aromatic hydrocarbons having 6 to 18 carbon atoms such as benzene and naphthalene; heterocyclic rings having 2 to 6 carbon atoms such as pyridine, pyrimidine, furan, thiophene, and pyrrole. Other rings such as cyclic ethers, lactones and lactams; and their derivatives are preferred. Among these, aromatic hydrocarbons and heterocyclic rings having a conjugated double bond exhibiting a high refractive index are preferable, and aromatic hydrocarbons having a rigid ring structure with less loss of mechanical strength to the resin are more preferable.
Among the above aromatic hydrocarbons, benzene and naphthalene are preferable, and benzene is more preferable.

The aromatic hydrocarbon, heterocycle, and other rings may have a condensed ring structure in the basic skeleton. Having a condensed ring structure is a form in which two or more ring structures are bonded so that two or more substitutable atoms in the ring structure in the basic skeleton constitute a part of a ring other than the ring structure. For example, when two adjacent carbon atoms constituting the thiophene ring of the thianaphthene skeleton constitute another benzene ring in addition to the benzene ring of the basic skeleton (formula (16) below), the benzene ring of the basic skeleton is There are cases where two adjacent carbon atoms constituting one another constitute a benzene ring in addition to the benzene ring of the basic skeleton to form naphthalene, which is a bicyclic condensed ring.
In addition, the said sulfur containing compound may have substituents other than the said substituents, such as an alkyl group, as needed.

The sulfur-containing compound of the present invention preferably has the above-described substituent, more preferably (1) a structure in which a halogen atom, a hetero atom, a deuterium atom, or a substituent having these atoms is bonded to the basic skeleton, And (2) at least one of the structures in which the aromatic hydrocarbon and the heterocyclic ring are condensed to the basic skeleton More preferably, the sulfur-containing compound is selected from the group consisting of (I) cyano group, nitro group, amino group, carbonyl group, halogen-substituted alkyl group, halogen atom, oxygen atom, sulfur atom, nitrogen atom and deuterium atom. A structure in which at least one atomic group or a substituent having an atom is bonded to the basic skeleton, and at least one of a benzene ring, a naphthalene ring, and a pyridine ring, which may have the substituents (II) and (I), The form having either or both of the structures condensed to the basic skeleton. These substituents are preferably those described above.

The structure of (I) may be any structure as long as the above-described atomic group or substituent having an atom is bonded to the basic skeleton, and the substituent may further have a substituent. You may have substituents other than a substituent. For example, a form in which an oxygen atom is bonded to a thianaphthene skeleton and a benzene ring is bonded to the oxygen atom is also included. In the structure of (I) above, the ring structure is such that two or more atoms in the basic skeleton form part of a ring other than the basic skeleton (for example, a ring having no conjugated double bond). It may be the structure of the formed form. As such a structure, for example, a compound represented by the following formula (10) is suitable.

As the compound having the above structure (I), for example, the following compounds are suitable as compounds having a thianaphthene skeleton (hereinafter also referred to as “thianaphthene-based”).
A thianaphthene-based thiophene ring with a substituent (for example, the following formula (4)), a thianaphthene-based benzene ring with a substituent (for example, the following formula (5)), a thianaphthene-based, Those with ether (for example, the following formula (6)), thianaphthene-based, with ketone (for example, the following formula (7)), thianaphthene-based, with an ester (for example, the following formula (8) )), A thianaphthene-based compound with naphthalene (for example, the following formula (9)).

As the compound having the above structure (I), for example, the following compounds are suitable as compounds having a phenyl disulfide skeleton (hereinafter also referred to as “disulfide type”).
A disulfide compound in which a sulfur atom of a phenyl disulfide skeleton and a carbon atom in the skeleton are bonded to a carbon atom of a benzene ring other than the phenyl disulfide skeleton to form a 6-membered ring (for example, the following formula (10)) A disulfide-based benzene ring having a halogen atom bonded thereto (for example, the following formulas (11) and (12)), a disulfide-based one having a benzene ring substituted by a deuterium atom (for example, the following formula ( 13)), disulfide-based ethers (for example, the following formula (14)), disulfide-based ones with naphthalene (for example, the following formula (15)), and the like.

Examples of the compound having the structure (II) include a thianaphthene-based compound in which benzene is condensed (for example, the following formula (16)), and a thianaphthene-based compound in which naphthalene is condensed (for example, the following formula ( 17)) and the like are preferable.

Examples of the compounds having the structures of (I) and (II) are, for example, thianaphthene-based compounds in which a benzene ring has a substituent and a benzene ring is condensed (for example, the following formula (18)), and thianaphthene-based compounds. And a benzene ring condensed and a thianaphthene skeleton and / or a condensed benzene ring substituted with a deuterium atom (for example, the following formula (19)) are preferable.

Among these, the above formulas (1), (3), (11), and (16) are more preferable, and (11) and (16) are more preferable.

The additive for resin may contain a compound other than the above compound as long as the effects of the present invention are exhibited. For example, an aromatic fluorine compound for the purpose of low moisture absorption is suitable. By adding these separately, moisture absorption can be reduced.

The present invention is also a resin composition comprising the resin additive. As described above, the resin composition has good compatibility with the resin, and includes an additive for a resin that can exhibit an excellent refractive index control function without impairing the strength of the resin. Excellent characteristics such as low transmission loss and bending loss can be exhibited. In addition to optical properties such as resin transparency, it has excellent properties such as mechanical properties and heat resistance, so it can withstand use in various environments, and can be used as an optical material such as an optical transmission body. It can be particularly suitably used for applications.

In the resin composition, the content ratio of the resin additive of the present invention is not particularly limited. For example, the sulfur-containing compound is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin. It is. If it is less than 1 part by weight, the refractive index may not be sufficiently controlled. If it exceeds 100 parts by weight, basic properties such as transparency and mechanical strength that the resin may have may not be sufficiently exhibited. More preferably, it is 1-80 weight part, More preferably, it is 1-70 weight part.

The resin composition is not particularly limited as long as it contains a resin. Among them, it is preferable that the resin composition contains a polymer that forms a molded article having transparency. Such a polymer only needs to form a molded article having transparency, and the resin composition containing the polymer contains, for example, a transparent resin such as an acrylic resin as described later. Those are particularly preferred.
Here, the transparency means having a high light transmittance, and the resin composition containing a polymer that forms a transparent molded product has a total light transmittance of 70% or more. It points to what is. The total light transmittance is preferably 75% or more, and more preferably 80% or more. Examples of the method for measuring the total light transmittance include a method using a colorimetric color difference meter NDH-1001DP type (manufactured by Nippon Denshoku Industries Co., Ltd.) as a measuring device.

As the molded product, fibers, molded products, films and the like are suitable. The fiber is a fibrous molded product, and the diameter is preferably 10 μm or more and 10,000 μm or less. The molded body is a molded product having a predetermined shape, for example, a molded body such as a pellet shape, a sheet shape such as a flat plate or a corrugated plate, a pipe shape; a semicircle, an L shape, a T shape, a U shape, a mountain shape, etc. An irregular shaped body having a shape of The film is a film or a sheet-like molded product, and the thickness is preferably 1 μm or more and 1000 μm or less.
As the molding method of the molded product, methods such as injection molding, extrusion molding, vacuum molding, blow molding, thermoforming, compression molding, calendar molding, powder molding, foam molding, laminate molding, and solvent casting are suitable.

As the transparent resin, acrylic resin, polycarbonate resin, fluorine resin, epoxy resin, polyether resin, polyester resin, polyarylate resin, polyimide resin, cycloolefin resin, silicon resin, norbornene Resins, polysulfone resins, polyketone resins, and the like are suitable, and one or more of these can be used. More preferred are acrylic resins and polycarbonate resins.
The acrylic resin is preferably one comprising a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid or an ester compound thereof as an essential component, for example, polymethyl methacrylate, Preference is given to polymethyl methacrylate, maleimide-modified polymethyl methacrylate, deuterated polymethyl methacrylate, etc. copolymerized with other types of monomers. A mixture or copolymer of these acrylic resins is also suitable.
The polycarbonate resin preferably includes a polymer having a carbonate bond (—O—CO—O—) in the main chain.

The resin composition of the present invention includes optical films used for substrates, antireflection layers, refractive index control layers, optical compensation layers, optical communication materials such as optical fibers and optical waveguides, optical switches, recording materials such as optical recording disks, The liquid crystal display, plasma display, digital paper, organic EL, inorganic EL, rear pro, etc. can be used particularly suitably for various optical material applications, such as optical pickup lenses, fθ for laser beam printers, etc. Lenses such as lenses, eyeglass lenses, camera lenses, video camera lenses, and lamp lenses; discs such as video discs, audio discs, and write-once discs for computers; optical transmission materials such as plastic optical fibers (POF), optical connectors, and light guides Etc. can be used. An optical fiber, an optical waveguide, an optical recording disk, an optical film, and a display substrate using such a resin composition of the present invention are also one preferred embodiment of the present invention.

The additive for a resin constituted by a compound having a sulfur atom and a benzene ring skeleton of the present invention has the above-described configuration and is refracted without impairing various characteristics such as a thermal characteristic of a resin such as a transparent resin. Since it can be suitably used for applications such as an additive capable of controlling the rate, it can be particularly suitably used for various optical material applications such as optical fibers, optical waveguides, optical recording disks, optical films, display substrates and the like. is there.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Example 1
The following formula (16) with respect to 2.0 g of polymethyl methacrylate (PMMA) dissolved in 18.0 g of chloroform;

0.4 g of dibenzothiophene represented by the formula was added. The film was obtained by casting on a glass plate and drying. The film was evaluated for thermal properties and refractive index. The results of thermal characteristics evaluation are shown in Table 1, and the refractive index results are shown in Table 2. In addition, thermal characteristic evaluation and refractive index measurement were measured by the following method.

Comparative Example 1
As a comparative example, the measurement was performed in the same manner as in Example 1 for a single PMMA.
Example 2
In place of dibenzothiophene, the following formula (11);

A film was obtained in the same manner as in Example 1 except that bis (4-chlorophenyl) disulfide represented by the following formula was used, and thermal characteristics evaluation and refractive index measurement of the film were performed. The results are shown in Tables 1 and 2.

(Thermal characteristics evaluation)
Using a Shimadzu differential thermogravimetric simultaneous measurement apparatus (manufactured by Shimadzu Corporation), the glass transition point and the weight reduction temperature (5 mass% reduction) were measured. The heating temperature was 10 ° C./min under a nitrogen atmosphere.

(Refractive index measurement)
Refractive indexes at 633 nm, 830 nm, 1310 nm, and 1550 nm were measured using a prism coupler SPA-4000 (manufactured by SAIRON TECHNOLOGY).

Claims (2)

An additive for a resin composed of a compound having a sulfur atom and a benzene ring skeleton,
The compound having a sulfur atom and a benzene ring skeleton is represented by the following formula (1);

A compound having an in thianaphthene bone skeleton represented in the molecule,
The additive for resin is used for controlling the refractive index of an optical material which is a molded article having transparency. A resin composition comprising the additive for resin according to claim 1 and an acrylic resin or a polycarbonate resin, and used for an optical material which is a molded article having transparency that requires refractive index control. object.