JP5648155B2 - Arylacetylene-containing resin, method for producing the same, and strain sensor using the resin - Google Patents

Description

  The present invention relates to an oligoarylacetylene-containing resin used for a strain sensor capable of measuring strain generated in a minute region of a component made of a Raman-inactive material using microscopic Raman spectroscopy, a method for producing the same, and a method using the same The present invention relates to a strain sensor, a strain sensor manufacturing solution, and a strain measurement method for a minute portion.

  From the viewpoint of improving product reliability and extending the service life, there is a high demand for stress / strain measurement in microscopic areas. Microscopic Raman spectroscopy has a high spatial resolution on the order of μm, and is therefore suitable for observing a minute part, and a specific Raman active material is used for measuring stress and strain in a minute part. Non-Patent Literature 1 and Non-Patent Literature 2 describe a strain measurement method using micro-Raman spectroscopy for a Raman-inactive material and a strain sensor used therefor.

According to the above document, the material used for this sensor is poly (diacetylene) (following formula (b)) by heating a film of a synthesized diacetylene-containing polymer (following formula (a)) at 100 ° C. for 40 hours. It is obtained by converting to.

In this document, the characteristics as a strain sensor are as follows: a polymer (b) is formed on the surface of a test piece, a Raman spectrum is measured while applying various forces to give a strain, and a change in the position of a peak derived from an acetylene moiety. It is evaluated by seeing.
Journal of Materials Science 27, 5958 (1992) Macromolecules 25, 684 (1992)

  However, in the method of forming a film by the above method, since the prepolymer film (a) must be prepared and heated for a long time of 40 hours at 100 ° C., the working environment and the like are greatly restricted. . For example, there are restrictions on objects such as large parts that do not enter the furnace and parts that cannot be removed cannot be processed. In addition, there is a restriction that it cannot be applied to parts having low heat resistance such as plastic.

  The present invention has been made in view of the above-mentioned conventional problems, and a novel oligoarylacetylene-containing resin capable of measuring strain and stress by a simplified process that does not require heating, a method for producing the same, It is an object of the present invention to provide a strain sensor using the same, a strain sensor manufacturing solution, and a strain measurement method for a minute portion.

（式中、Ｒ_１〜Ｒ_４はそれぞれ独立に置換されていてもよいアリール基、アルキル基、アルコキシ基、アリーロキシ基または水素原子を示し、ｍは正の整数である。）

（式中、Ｒ_５は樹脂化合物を構成する高分子鎖を示す。）

（式中、Ｒ_６は置換されていてもよい二価のアルキル基、または置換されていてもよい二価のアリール基を示す。） As a result of intensive studies to solve the above problems, the present inventors have found that an oligoarylacetylene represented by the following general formula (1), a resin compound represented by the general formula (2), and a general formula (3) It was found that a polymer having three components of diisocyanate represented by formula (1) as a monomer meets the above conditions. This compound can be suitably used as a sensor because a triple bond-derived signal appears strongly in Raman spectrum measurement. When this polymer is formed into a film, intermolecular π-π stacking occurs, and therefore the orientation can be controlled without heating as a post-treatment after film formation.

(In the formula, R _{1 to} R ₄ each independently represents an aryl group, an alkyl group, an alkoxy group, an aryloxy group, or a hydrogen atom which may be substituted, and m is a positive integer.)

(In the formula, R ₅ represents a polymer chain constituting the resin compound.)

(In the formula, R ₆ represents an optionally substituted divalent alkyl group or an optionally substituted divalent aryl group.)

（式中、Ｒ_１〜Ｒ_４はそれぞれ独立に置換されていてもよいアリール基、アルキル基、アルコキシ基、アリーロキシ基または水素原子を示し、ｍは正の整数である。Ｒ_５は樹脂化合物を構成する高分子鎖を示す。Ｒ_６は置換されていてもよい二価のアルキル基または置換されていてもよい二価のアリール基を示し、ｐは共重合の割合で０＜ｐ≦１であり、ｎは平均重合度である。） The polymer having three components of the oligoarylacetylene represented by the general formula (1), the resin compound represented by the general formula (2), and the diisocyanate represented by the general formula (3) is represented by the following general formula: It is represented by Formula (4).

(Wherein R _{1 to} R ₄ each independently represents an optionally substituted aryl group, alkyl group, alkoxy group, aryloxy group or hydrogen atom, m is a positive integer. R ₅ represents a resin compound. And R ₆ represents a divalent alkyl group which may be substituted or a divalent aryl group which may be substituted, and p represents a copolymerization ratio of 0 <p ≦ 1. And n is the average degree of polymerization.)

（式中、Ｒ_１〜Ｒ_４はそれぞれ独立に置換されていてもよいアリール基、アルキル基、アルコキシ基、アリーロキシ基または水素原子を示し、ｍは正の整数である。Ｒ_６は置換されていてもよい二価のアルキル基または置換されていてもよい二価のアリール基を示す。）

（Ｒ_５は樹脂化合物を構成する高分子鎖を示し、Ｒ_６は置換されていてもよい二価のアルキル基または置換されていてもよい二価のアリール基を示す。） The copolymer represented by the general formula (4) is composed of a unit (I) in which an oligoarylacetylene and an isocyanate are bonded, and a unit (II) in which a resin compound and an isocyanate are bonded. Unit (I) and unit (II) may be bonded alternately or randomly.

(In the formula, R _{1 to} R ₄ each independently represents an aryl group, an alkyl group, an alkoxy group, an aryloxy group, or a hydrogen atom, which may be substituted, and m is a positive integer. R ₆ is substituted. A divalent alkyl group which may be substituted or a divalent aryl group which may be substituted.

(R ₅ represents a polymer chain constituting the resin compound, and R ₆ represents an optionally substituted divalent alkyl group or an optionally substituted divalent aryl group.)

Examples of the alkyl group represented by R _{1 to} R ₄ in the general formula (1) and the general formula (4) include methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, n-, Examples thereof include linear, branched and cyclic alkyl groups having 1 to 24, preferably 1 to 12, carbon atoms such as iso- or neo-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and the like. Examples of the aryl group include phenyl groups, o-, m-, p-tolyl groups, 1- and 2-naphthyl groups, anthryl groups, fluorenyl groups and the like, and aryl groups having 6 to 50 carbon atoms, preferably 6 to 32 carbon atoms. It is done.

Examples of the alkoxy group represented by R _{1 to} R ₄ in the general formula (1) and the general formula (4) include methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, Examples thereof include linear, branched, and cyclic alkoxy groups having 1 to 24, preferably 1 to 12, carbon atoms such as iso- or neo-pentoxy, n-hexoxy, cyclohexoxy, n-heptoxy, n-octoxy and the like. Examples of the aryloxy group include aryloxy groups having 6 to 50 carbon atoms, preferably 6 to 32 carbon atoms such as phenoxy group, o-, m-, p-triloxy group, 1- and 2-naphthoxy group, anthoxy group and fluorenyl group. It is done.

In the general formula (3) and general formula (4), examples of the divalent alkyl group represented by R ₆ include methylene, ethane-1,2-diyl, ethane-1,1-diyl, propane-1, Examples thereof include linear and branched divalent alkyl groups having 1 to 20, preferably 2 to 8, carbon atoms such as 1-diyl, propane-1,2-diyl and propane-1,3-diyl.

In the general formulas (3) and (4), examples of the divalent aryl group represented by R ₆ include o-phenylene, p-phenylene, thiophene-2,5-diyl, thiophene-2, 3-diyl, pyridine-2,5-diyl, pyridine-2,3-diyl, pyridine-4,5-diyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-1,2- Diyl, naphthalene-1,7-diyl, anthracene-9,10-diyl, anthracene-1,4-diyl, anthracene-2,6-diyl, anthracene-1,7-diyl, biphenylene-4,4′-diyl , Fluorene-2,7-diyl, diphenylmethane-4,4′-diyl, and compounds in which the aromatic ring of these aromatic compounds is substituted are also included.

In the general formulas (3) and (4), examples of the compound in which the aromatic ring of the divalent aryl group represented by R ₆ is substituted include alkoxybenzene-1,4-diyl, alkylbenzene- 1,4-diyl, arylbenzene-1,4-diyl, aryloxybenzene-1,4-diyl, 2,5-, 2,3-, 2,6-dialkoxybenzene-1,4-diyl, 2 , 3,5-trialkoxybenzene-1,4-diyl, 2,3,5,6-tetraalkoxybenzene-1,4-diyl, 2,5-, 2,3-, 2,6-dialkylbenzene 1,4-diyl, 2,3,5-trialkylbenzene-1,4-diyl, 2,3,5,6-tetraalkylbenzene-1,4-diyl, 2,5-, 2,3-, 2, 6-Diarylbenzene-1,4-dii 2,3,5-triarylbenzene-1,4-diyl, 2,3,5,6-tetraarylbenzene-1,4-diyl, 2,5-, 2,3-, 2,6- Diallyloxybenzene-1,4-diyl, 2,3,5-triallyloxybenzene-1,4-diyl, 2,3,5,6-tetraaryloxybenzene-1,4-diyl, alkoxythiophene- 2,5-diyl, alkylthiophene-2,5-diyl, arylthiophene-2,5-diyl, aryloxythiophene-2,5-diyl, dialkoxythiophene-2,5-diyl, dialkylthiophene-2,5 -Diyl, diarylthiophene-2,5-diyl, diaryloxythiophene-2,5-diyl, 9,9-dialkoxyfluorene-2,7-diyl, 9,9-diaryl Fluorene-2,7-diyl, etc. 9,9-aryloxy-2,7-diyl.

In the general formulas (1) to (4), R _{1 to} R ₄ and R ₆ may have a substituent which may be substituted as long as it does not participate in the polymerization reaction described below. Examples include the aforementioned alkoxy group, alkyl group, aryl group, and aryloxy group.

The polymer chain constituting the resin compound represented by R ₅ can be used as long as it is composed of a polymer having a functional group for chemically bonding with an isocyanate compound. Examples of such a base polymer include polymers having a carboxy group, an amino group, or a hydroxy group at the terminal, such as a polyester resin and a polyamide resin. These resins can bond a crosslinking agent to their terminal functional groups. Examples of such resins include polyethylene glycol, polypropylene glycol, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, nylon 6, nylon 66, nylon 11, nylon 12, nylon-MXD 6 and the like. . In addition, a biodegradable polymer having a functional group for chemically bonding can be used as the base polymer. Examples of such biodegradable polymers include polylactic acid, starch, cellulose acetate, (chitosan / cellulose / starch), polycaprolactone, polybutylene succinate, polyethylene succinate, poly (butylene succinate / adipate), poly (Butylene succinate / carbonate), polyethylene succinate, poly (butylene succinate / terephthalate), polyvinyl alcohol, poly (hydroxybutyrate / hydroxyvalerate) and the like.

  The resin compound represented by the general formula (4) includes oligoarylacetylene diol (the general formula (1)), a resin compound (the general formula (2)), and a divalent isocyanate (the general formula (3)). Can be obtained by dissolving in a solvent and carrying out a heating reaction. The reaction in this case is represented by the formula (c).

（式中、Ｒ_１〜Ｒ_４はそれぞれ独立に置換されていてもよいアリール基、アルキル基、アルコキシ基、アリーロキシ基または水素原子を示し、ｍは正の整数である。Ｒ_５は樹脂化合物を構成する高分子鎖を示す。Ｒ_６は置換されていてもよい二価のアルキル基または置換されていてもよい二価のアリール基を示し、ｐは共重合の割合で０＜ｐ≦１であり、ｎは平均重合度である。）

(Wherein R _{1 to} R ₄ each independently represents an optionally substituted aryl group, alkyl group, alkoxy group, aryloxy group or hydrogen atom, m is a positive integer. R ₅ represents a resin compound. And R ₆ represents a divalent alkyl group which may be substituted or a divalent aryl group which may be substituted, and p represents a copolymerization ratio of 0 <p ≦ 1. And n is the average degree of polymerization.)

  In this polymerization, various solvents usually used in this kind of reaction can be used. Examples thereof include N, N-dimethylformamide (DMF), toluene, tetrahydrofuran (THF) and the like.

  In the general formulas (4) and (c), p is the introduction rate of oligoarylacetylene and can take any value of 0 <p ≦ 1.

  In the general formulas (4) and (c), n is an average degree of polymerization and can take any value of 1 <n.

  Using the oligoarylacetylene-containing resin of the present invention, it can be attached to the surface of the object to be measured and used as a strain sensor. That is, the method for measuring strain of a minute portion according to the present invention includes a first step of sticking the oligoarylacetylene-containing resin of the present invention to the surface of a measured object to form a strain sensor, and applying stress or strain to the measured object. And a second step of measuring a Raman spectrum at a predetermined position of the strain sensor attached to the object to be measured.

  In order to stick the oligoarylacetylene-containing resin to the surface of the object to be measured, the oligoarylacetylene-containing resin of the present invention is dissolved in a solvent to form a strain sensor preparation solution, which is applied to the surface of the object to be measured and dried. Can be done. The oligoarylacetylene-containing resin of the present invention can be easily dissolved in an ordinary organic solvent such as halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform, organic acids such as trifluoroacetic acid, toluene, THF and DMF without crystallization. Therefore, since it can be easily formed into a film by using a normal coating method such as a spin coating method, a dip coating method, a roll coating method, etc., it can be used as a constituent material of a strain sensor. .

  According to the present invention, since the strain sensor film can be attached to the measurement object without heating the measurement object, it is not necessary to put the measurement object in the furnace, and the dimensions and materials of the object This restriction is removed. For this reason, it is possible to measure strains of minute portions of members of various shapes and materials. Further, since the strain sensor can be formed at the site where the object is used and at any part of the member, the strain generated in the actual part can be measured in an actual load state.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.

Example 1
(Synthesis of m = 2 arylacetylene-containing resin)
Under a nitrogen atmosphere, 401 mg of polypropylene glycol having hydroxy groups at both ends (general formula (2), R ₅ = polypropylene glycol, molecular weight 400) and 1,4-bis {(4-hydroxymethylphenyl) ethynyl} benzene (general formula (1), R ₁ = R ₂ = R ₃ = R ₄ = Hydrogen atom, m = 2) In a solution of 339 mg in 5 mL of DMF, 4,4′-diphenylmethane diisocyanate (general formula (3), R ₆ = Diphenylmethane-4,4′-diyl) (501 mg) was added, and the mixture was stirred in an oil bath at 100 ° C. for 24 hours. Thereafter, the powder deposited by pouring the reaction solution into water is filtered and dried under reduced pressure to give resin 1 (general formula (4), R ₅ = polypropylene glycol, R ₆ = diphenylmethane-4,4′-diyl, R ₁ = R ₂ = R ₃ = R ₄ = hydrogen atom, m = 2, p = 0.5) was obtained as 1.01 g of white powder. Resin 1 showed high solubility in DMF and was partially soluble in chloroform.

The absorption peak wave number of the IR spectrum of the obtained resin 1 is as follows. 3333, 2940, 2867, 1727, 1597, 1531, 1511, 1459, 1413, 1376, 1308, 1217, 1160, 1104, 1060, 1017, 915, 838, 817, 767, 735, 635, 615 cm ⁻¹

The number average molecular weight of the chloroform soluble part of the obtained resin 1 was 2400 (n = 1.9), and the weight average molecular weight was 4100 (n = 3.3). The peak wave number derived from C≡C in the Raman spectrum of the obtained resin 1 was 2212 cm ⁻¹ .

(Evaluation of sensing characteristics of resin)
Resin 1 was dissolved in DMF and cast into a metal plate. After the film was naturally dried, the metal plate was bent, and the Raman spectrum was measured while applying tensile strain to the film, thereby examining the characteristics as a strain sensor.

The peak wave number derived from C≡C in the Raman spectrum of the resin 1 before bending the metal plate was 2212 cm ⁻¹ , whereas the Raman spectrum of the resin 1 in a state where the metal plate was bent was measured. The derived peak wave number was 2208 cm ⁻¹ , confirming the movement of the peak wave number due to strain.

Example 2
(Synthesis of Arylacetylene-Acetylene-Containing Resin with m = 1)
Under a nitrogen atmosphere, 313 mg of polycaprolactone having a hydroxy group at both ends (general formula (2), R ₅ = polycaprolactone, molecular weight: 1250) and 125 mg of 4,4′-diphenylmethane diisocyanate (general formula (3), R ₆ = diphenylmethane-4,4′-diyl), 60 mg of bis (4-hydroxymethylphenyl) acetylene (general formula (1), R ₁ = R ₂ = R ₃ = R ₄ = hydrogen atom, m = 1) It melt | dissolved in 5 mL DMF and stirred at 100 degreeC for 72 hours. Thereafter, the powder precipitated by pouring the reaction solution into methanol is filtered and dried under reduced pressure, whereby resin 2 containing acetylene (general formula (4), R ₅ = polycaprolactone, R ₆ = diphenylmethane-4,4). '-Diyl, R ₁ = R ₂ = R ₃ = R ₄ = hydrogen atom, m = 1, p = 0.5) was obtained as 138 mg of white powder. Resin 2 showed high solubility in DMF and was partially soluble in chloroform.

The absorption peak wave number of the IR spectrum of the obtained resin 2 is as follows. 3311,3033,2941,2868,1729,1642,1593,1537,1510,1463,1413,1378,1304,1221,1201,1160,1107,1060,1017,915,857,815,769,639cm ^-1

The number average molecular weight of the chloroform soluble part of the obtained resin 2 was 5100 (n = 2.6), and the weight average molecular weight was 8900 (n = 4.5). The peak wave number derived from C≡C of the Raman spectrum was 2214 cm ⁻¹ .

(Evaluation of sensing characteristics of resin)
After the resin 2 was dissolved in DMF and cast onto a substrate to form a film, the characteristics as a strain sensor were examined in the same manner as in Example 1.

Resin in a state where the metal plate is bent while the peak wave number derived from C≡C of the Raman spectrum of the resin 2 before being bent is 2214 cm ⁻¹ (see FIG. 1). When the Raman spectrum of No. 2 was measured, the peak wave number derived from C≡C was 2211 cm ⁻¹ (see FIG. 2), and movement of the peak wave number due to strain was confirmed (see FIG. 3).

  When a metal wire was used as a substrate and the relationship between the magnitude of the strain when strain was applied and the change in the peak wave number of the resin 2 was examined, a linear relationship as shown in FIG. 4 was shown.

2 is a Raman spectrum of Resin 2 synthesized in Example 2. A solid line is an actual measurement value, and a dotted line is a curve fit based on the actual measurement value. It is a Raman spectrum of the resin 2 in the state apply | coated to the metal plate and bent in Example 2. FIG. A solid line is an actual measurement value, and a dotted line is a curve fit based on the actual measurement value. 3 is a comparison of the curve-fitted spectra in FIG. 1 and FIG. The solid line is before bending, and the dotted line is in the bent state. 6 is a graph showing the relationship between the magnitude of strain and the change in the peak wave number of resin 2 when strain is applied to a metal wire in Example 2.

Claims (10)

An arylacetylene-containing resin obtained by copolymerizing an oligoarylacetylene diol represented by the following general formula (1), a resin compound represented by the general formula (2), and a diisocyanate represented by the general formula (3).

(In the formula, R _{1 to} R ₄ each independently represents an aryl group, an alkyl group, an alkoxy group, an aryloxy group, or a hydrogen atom which may be substituted, and m is a positive integer.)

(In the formula, R ₅ represents a polymer chain constituting the resin compound.)

(In the formula, R ₆ represents an optionally substituted alkylene group or an optionally substituted arylene group.) An oligoarylacetylene-containing resin compound represented by the following general formula (4).

(Wherein R _{1 to} R ₄ each independently represents an optionally substituted aryl group, alkyl group, alkoxy group, aryloxy group or hydrogen atom, m is a positive integer. R ₅ represents a resin compound. R ₆ represents an alkylene group which may be substituted or an arylene group which may be substituted, p represents a copolymerization ratio of 0 <p ≦ 1, and n represents an average polymerization Degrees.) 3. The oligoarylacetylene-containing resin according to claim 1, wherein m = 1 or m = 2 in the general formula (1) and the general formula (4). 3. The oligoarylacetylene-containing resin according to claim 1, wherein in the general formula (2) and the general formula (4), R ₅ is a polyoxyalkylene chain or a polyester chain. Formula (3) and general formula (4), oligoaryl acetylene-containing resin according to any one of claims 1 to 2, characterized in that R 6 ₌ 4,4'-diphenylmethyl group. The oligoaryl acetylenic diol represented by the general formula (1), a resin compound having both ends represented by a hydroxy group represented by the general formula (2), and a diisocyanate compound represented by the general formula (3) are copolymerized. A method for producing the resin according to any one of 1 to 2. A strain sensor comprising the arylacetylene-containing resin according to any one of claims 1 to 5, and being attached to a surface of an object to be measured. A solution for preparing a strain sensor, wherein the arylacetylene-containing resin according to any one of claims 1 to 5 is dissolved in a solvent.   A first step of attaching the strain sensor of claim 7 to the object to be measured, and measuring a Raman spectrum at a predetermined position of the strain sensor attached to the object to be measured while applying stress to the object to be measured. And a second step. A method for measuring strain of a minute portion, comprising: a second step.   The method for measuring strain of a minute part according to claim 9, wherein the first step is performed by applying the solution for preparing a strain sensor according to claim 8 to the surface of the object to be measured and drying it.

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