JP2019094382A - Resin composition - Google Patents

Abstract

To provide a resin composition excellent in dilatancy.SOLUTION: A resin composition (X) contains a resin (A) whose storage elastic modulus (E') in dynamic viscoelasticity satisfies the following expressions 1 to 2: [Condition 1] storage elastic modulus (E'1000) at oscillation frequency of 1,000 Hz/storage elastic modulus (E'1) at oscillation frequency of 1 Hz of 20 or more; and [Condition 2] storage elastic modulus (E'0.1) at oscillation frequency of 0.1 Hz=10to 10Pa, preferably of 5×10to 5×10Pa, and further preferably of 10to 10Pa.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition excellent in dilatancy.

  Resins having dilatancy properties are used in various applications such as anti-vibration rubber and medical supplies (for example, Patent Document 1).

Unexamined-Japanese-Patent No. 5-320305

  However, even with the technology of Patent Document 1 mentioned above, it can not be said that dilatancy can be sufficiently satisfactory, and further improvement has been desired. An object of the present invention is to provide a resin composition excellent in dilatancy.

The present inventors arrived at the present invention as a result of studying to achieve the above object. That is, the present invention is a resin composition (X) formed by containing a resin (A) in which storage elastic modulus (E ′) in dynamic viscoelasticity satisfies the following conditions 1 to 2.
<Condition 1>
Storage elastic modulus at a vibration frequency of 1000 Hz (E'1000) / storage elastic modulus at 1 Hz (E'1) of 20 or more <Condition 2>
Storage modulus at an oscillation frequency of 0.1 Hz (E'0.1) = 1 x 10 ⁵ to 1 x 10 ⁸ Pa

The resin composition (X) of the present invention exhibits the following effects.
(1) Excellent in dilatancy.
(2) Excellent in resin strength and flexibility (followability).

<Resin (A)>
In the resin (A) of the present invention, the storage elastic modulus (E ′) in dynamic viscoelasticity satisfies the following conditions 1 to 2.
In the present invention, the storage elastic modulus (E ′) is measured using a dynamic viscoelasticity measuring apparatus (DMA, manufactured by Anton Paar) in the longitudinal direction, which is the longitudinal direction of the film, and the transverse direction, which is orthogonal to the longitudinal direction. It is the value which measured the viscoelastic behavior to temperature 25 ° C, distortion 1%, vibration frequency 0.1-1000 Hz (unit: Pa).

<Condition 1>
Storage elastic modulus at a vibration frequency of 1000 Hz (E'1000) / storage elastic modulus at 1 Hz (E'1) of 20 or more.
If the above (E'1000) / (E'1) is less than 20, dilatancy is insufficient.
Further, (E'1000) / (E'1) is preferably 30 or more, more preferably 40 or more, and particularly preferably 50 or more.

<Condition 2>
Storage modulus at an oscillation frequency of 0.1 Hz (E′0.1) = 1 × 10 ⁵ to 1 × 10 ⁸ Pa.
When the above (E'0.1) is less than 10 ⁵ Pa, the resin strength is insufficient, and when it is more than 10 ⁸ Pa, the flexibility is insufficient.
Further, the (E'0.1) is preferably ^{5 × 10 5 ~5 × 10 7} Pa, more preferably 10 ⁶ ~10 ⁷ Pa.

  Various resins may be mentioned as the resin (A), but preferred are polyester (A1) and polyurethane (A3) described later, and more preferred is polyurethane (A3).

The weight average molecular weight (Mw) of the above (A) is preferably 10,000 to 300,000, more preferably 20,000 to 250,000.
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC).

<GPC measurement conditions>
-Device: "GPC-104" (manufactured by shodex)
・ Column: "KD-806M" (two), "KD-802" (all from Shodex Co., Ltd.)
Sample solution: 0.125% by weight of N, N-dimethylformamide solution Injection amount of solution: 10 μL
Flow rate: 0.6 mL / min Measurement temperature: 40 ° C.
Detection device: Refractive index detector Reference substance: Standard polystyrene (manufactured by Tosoh Corp.)

<Polyester (A1)>
The polyester (A1) in the present invention is formed by polycondensation of a monomer containing a diol (a1) described later and a dicarboxylic acid (b1) as a constituent monomer. From the viewpoint of dilatancy, it is preferable to further contain a tricarboxylic acid (b2) as a constituent monomer.

As the diol (a1), for example, aliphatic alcohol [linear alcohol [having a carbon number (hereinafter, may be abbreviated as C) 2 to 10, for example, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol (hereinafter abbreviated as EG, DEG, 1,3-PG, 1,4-BD, 1,5-PD, 1,6-HD, respectively) Alcohols with branched chain [1,2-propylene glycol, neopentyl glycol (hereinafter abbreviated as 1,2-PG, NPG, respectively), 3-methyl-1,5-pentanediol, 2,2-diethyl- 1,3-propanediol, 1,2-, 1,3- and 2,3-butanediol etc.]]; and alcohols having a ring [C 8 or more and Mn Less than 00, for example, an alicyclic alcohol containing [1,4-bis (hydroxymethyl) cyclohexane, etc.], araliphatic alcohols (m-and p- xylylene glycol and the like) and the like] and the like.
Among the above (a1), preferred are aliphatic alcohols, more preferred are aliphatic alcohols having 2 to 4 carbon atoms, and particularly preferred is propylene glycol.

As the dicarboxylic acid (b1), aliphatic [carbon number (hereinafter abbreviated as C) 3 to 30, such as succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarballylic acid], Aromatic [C8-30, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, and alicyclic-containing polycarboxylic acids [C6-50, such as 1,3-cyclobutanedicarboxylic acid, 1,3-cyclo] Pentanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane, dicyclohexyl-4,4′-dicarboxylic acid, dimer acid]; polycarboxylic acids thereof Ester-forming derivatives [acid anhydride (maleic anhydride, phthalic anhydride, etc.), lower alkyl (C1-4) ester [Dimethyl ester (dimethyl terephthalate, etc.), diethyl ester (diethyl maleate etc., etc.], acid halides (terephthalic acid dichloride etc.), etc.] Dicarboxylic acids (b1) include oxalic acid, malonic acid, succinic acid, glutar Acid, adipic acid, pimelic acid, suberic acid, azeleic acid, sebacic acid, sephalic acid, orthophthalic acid, isophthalic acid, terephthalic acid, t-butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc. It can be mentioned.
Among the above (b1), aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and adipic acid and terephthalic acid are more preferable.

  Examples of tricarboxylic acids (b2) include trimellitic acid (anhydride).

The polyester (A1) can be produced by subjecting a constituent monomer containing a diol (a1), a dicarboxylic acid (b1) and a tricarboxylic acid (b2) to an esterification reaction.
Moreover, in order that (A1) satisfy | fills the said conditions 1-2, the following method is mentioned, for example.
(1) Adjust the degree of crosslinking by (b2).
(2) Adjust the esterification rate.
(3) The weight ratio [(b2) / {(a1) + (b1)}] preferably undergoes esterification reaction at 0.5 / 100 to 2/100.

<Polyurethane (A3)>
The polyurethane (A3) in the present invention comprises a polyester (A2) formed by polycondensation of a monomer containing a diol (a1) and a dicarboxylic acid (b1) as a constituent monomer, and a diisocyanate (c). The polyurethane (A3) formed by reacting the constituent materials contained therein as a urethane group concentration based on the weight of (A3) is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight .
The said urethane group density | concentration can be suitably adjusted with the kind of (c), and weight.

As (a1) and (b1) in the polyester (A2), those similar to the above-mentioned polyester (A1) can be mentioned, and preferred ones are also the same.
Moreover, as for (A2), it is also the same as (A1) that it is preferable to further constitute the tricarboxylic acid (a2) as a constituent monomer.
Furthermore, the rest is the same as the polyester (A1).

  (I) Aliphatic diisocyanates [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate (i) (i) (i) carbon number (excluding carbon in NCO group, the same applies hereinafter) 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl -2, 6-diisocyanato hexanoate etc];

(Ii) Alicyclic diisocyanate having 4 to 15 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene etc.];

(Iii) aromatic aliphatic diisocyanates having 8 to 15 carbon atoms (m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'- tetramethyl xylylene diisocyanate (TMXDI), etc .; Specific examples of group polyisocyanates are 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and And / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4', 4 ''-triphenylmethane (Ii) modified products of these diisocyanates (modified diisocyanates having a carbodiimide group, a uretdione group, a uretimine group, a urea group, etc.); and two or more of these A mixture of

  Among the above (c), aliphatic diisocyanates and alicyclic diisocyanates are preferred, and HDI, IPDI and hydrogenated MDI are more preferred, and IPDI is particularly preferred.

  The polyurethane (A3) can be produced, for example, by the urethanization reaction of the polyester (A2) and the diisocyanate (c).

<Resin composition (X)>
The resin composition (X) of the present invention comprises the resin (A). The resin composition (X) may contain, in addition to the resin (A), known additives for resins, compounding materials, solvents, and the like, as long as the effects of the present invention are not impaired.

<Molded item>
The molded article of the present invention is formed by molding the resin composition (X). Moreover, after apply | coating the solution melt | dissolved in the solvent, the solvent may be removed.

The resin composition (X) and the molded article thereof of the present invention are excellent in dilatancy when the resin (A) satisfies the conditions 1 and 2. For this reason, for example, it is possible to follow a slow deformation speed (flexibility is large), and it is considered that it becomes hard when an impact is applied and it is possible to exhibit resin strength.
Therefore, it can be suitably used for various applications, adhesives, cushioning materials, vibration proofing materials, daily goods (for example, sports goods), medical goods, and the like.

  Hereinafter, the present invention will be further described by way of examples and comparative examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates% by weight and parts indicate parts by weight.

<Production Example 1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet pipe, 640 parts of propylene glycol, 260 parts of terephthalic acid, 404 parts of adipic acid, 9.7 parts of trimellitic anhydride, dibutyltin oxide (DBTO) 2 as a catalyst. Five parts were charged, and the temperature was raised to 180 ° C. over 3 hours while distilling off propylene glycol and water under nitrogen gas aeration.
Next, the temperature was raised to 220 ° C. in a nitrogen atmosphere over 2 hours, and the reaction was continued at 220 ° C.
Furthermore, when the acid value of the contents was less than 10, the reaction was performed under a reduced pressure of 0.5 to 2.5 kPa. During the reaction under reduced pressure, return to normal pressure every 20 minutes, measure the molecular weight of the contents, continue the reaction under reduced pressure again, and when the weight average molecular weight (Mw) reaches 53,000, take out and remove Resin (polyester) (A-1) was obtained.

<Production Examples 2 to 6, Comparative Production Examples 1 and 2>
Each resin (polyester) (A) was obtained in the same manner as in Production Example 1 except that the production example 1 was according to Table 1. The results are shown in Table 1.

Production Example 7
In a pressure-resistant reaction vessel equipped with a stirrer, heating / cooling device and thermometer, 440 parts of resin (polyester) (A-1), 4.4 parts of isophorone diisocyanate (IPDI), and 1060 parts of N, N-dimethylformamide are charged and sealed. In the state, the reaction was carried out at 80 ° C. for 6 hours to obtain a solution of a resin (polyurethane) (A-7) containing a hydroxy group at an end.
The urethane group concentration of the resin (A-7) was 0.58%, and the weight average molecular weight was 180,000.

<Production Examples 8 to 10, Comparative Production Example 3>
A solution of each resin (polyurethane) (A) was obtained in the same manner as in Production Example 7 except that production example 7 was carried out according to Table 2. The results are shown in Table 2.

<Examples 1 to 3, Comparative Example 1>
Each resin composition (X) was obtained using resin (A-4)-(A-6) and (ratio A-1) of Table 3 as it was.
Each obtained resin composition (X) was pressurized by 130 degreeC and 1 MPa conditions with a heat press, and the film with a thickness of 300 micrometers was obtained. The results are shown in Table 3.

Examples 4 to 7 and Comparative Example 2
The solution of resin (A-7)-(A-10) of Table 3 and (ratio A-3) was used as it was, and each resin composition (X) was obtained.
Each obtained resin composition (X) was dried under a reduced pressure of 120 ° C., and then pressurized with a heat press at 130 ° C. and 1 MPa to obtain a film of 300 μm in thickness. The results are shown in Table 3.

  From the results of Tables 1 to 3, the resin composition (X) of the present invention has a storage elastic modulus in a low frequency region in a specific range and a high frequency dependence of the storage elastic modulus as compared with those of the comparison. is there. From this, it is considered to be excellent in dilatancy and excellent in resin strength and flexibility (followability).

  The resin composition (X) of the present invention and the molded article thereof are excellent in dilatancy and excellent in flexibility (high followability), and exhibit excellent resin strength when impact is further applied. Therefore, it is extremely useful because it can be suitably used in various applications, adhesives, cushioning materials, vibration-damping materials, daily goods (for example, sports goods), medical goods and the like.

Claims (4)

Resin composition (X) formed by containing resin (A) in which storage elastic modulus (E ') in dynamic viscoelasticity satisfies the following conditions 1-2.
<Condition 1>
Storage elastic modulus at a vibration frequency of 1000 Hz (E'1000) / storage elastic modulus at 1 Hz (E'1) of 20 or more <Condition 2>
Storage modulus at an oscillation frequency of 0.1 Hz (E'0.1) = 1 x 10 ⁵ to 1 x 10 ⁸ Pa   The said resin (A) is polyester (A1) formed by polycondensing the monomer which contains diol (a1), dicarboxylic acid (b1), and tricarboxylic acid (b2) as a structural monomer. Resin composition.   The resin (A) contains, as a constituent raw material, a polyester (A2) formed by polycondensation of a monomer containing a diol (a1) and a dicarboxylic acid (b1) as a constituent monomer, and a diisocyanate (c) The resin composition according to claim 1, which is a polyurethane (A3) formed by reacting constituent materials and having a urethane group concentration of 0.1 to 10% by weight based on the weight of (A3).   The molded object which shape | molded the resin composition (X) in any one of Claims 1-3.