JP7058982B2 - Resin composition - Google Patents

Description

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

Dilatancy resins are used in various applications such as anti-vibration rubber and medical supplies (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 5-320305

However, even with the technique of Patent Document 1, it cannot be said that the dilatancy is sufficiently satisfactory, and further improvement is required. An object of the present invention is to provide a resin composition having excellent dilatancy.

The present inventors have arrived at the present invention as a result of studies for achieving the above object. That is, the present invention is a film obtained by molding a resin composition (X) containing a resin (A) having a storage elastic acid (E') in dynamic viscoelasticity satisfying the following conditions 1 and 2 below. The resin (A) contains polyester (A2) obtained by polycondensing a monomer containing a diol (a1) and a dicarboxylic acid (b1) as constituent monomers, and diisocyanate (c) as constituent raw materials. It is a polyurethane (A3) formed by reacting a constituent raw material, and is a film formed by molding a resin composition (X) having a urethane group concentration of 0.1 to 10% by weight based on the weight of (A3).
<Condition 1>
Storage elastic modulus (E'1000) at vibration frequency 1000 Hz / storage elastic modulus (E'1) at 1 Hz is 20 or more <Condition 2>
Storage elastic modulus at vibration frequency 0.1 Hz (E'0.1) = 1 × 10 ⁵ to 1 × 10 ⁸ Pa

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

<Resin (A)>
The resin (A) in the present invention has a storage elastic modulus (E') in dynamic viscoelasticity satisfying the following conditions 1 and 2.
In the present invention, the storage elastic modulus (E') is determined by using a dynamic viscoelasticity measuring device (DMA, manufactured by Antonio Par) in the longitudinal direction, which is the longitudinal direction of the film, and the lateral direction orthogonal to the direction. , Temperature 25 ° C., strain 1%, viscoelastic behavior from vibration frequency 0.1 to 1000 Hz (unit: Pa).

<Condition 1>
The storage elastic modulus (E'1000) at a vibration frequency of 1000 Hz / the storage elastic modulus (E'1) at 1 Hz is 20 or more.
If the above (E'1000) / (E'1) is less than 20, the 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 elastic modulus (E'0.1) at a vibration frequency of 0.1 Hz = 1 × 10 ⁵ to 1 × 10 ⁸ Pa.
If the above (E'0.1) is less than 10 ⁵ Pa, the resin strength is insufficient, and if it exceeds 10 ⁸ Pa, the flexibility is insufficient.
Further, the above (E'0.1) is preferably 5 × 10 ⁵ to 5 × 10 ⁷ Pa, and more preferably 10 ⁶ to 10 ⁷ Pa.

Examples of the resin (A) include various resins, but polyester (A1) and polyurethane (A3) described later are preferable, and polyurethane (A3) is more preferable.

The weight average molecular weight (Mw) of (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 Co., Ltd.]
-Columns: "KD-806M" (2 pieces), "KD-802" [both manufactured by shodex Co., Ltd.]
-Sample solution: 0.125% by weight N, N-dimethylformamide solution-Solution injection amount: 10 μL
・ Flow rate: 0.6mL / min ・ Measurement temperature: 40 ℃
・ Detection device: Refractive index detector ・ Reference material: Standard polystyrene [manufactured by Tosoh Corporation]

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

Examples of the diol (a1) include aliphatic alcohols [straight-chain alcohols [carbon numbers (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) ] Etc.; Alcohols with branched chains [1,2-propylene glycol, neopentyl glycol (hereinafter abbreviated as 1,2-PG and NPG, respectively), 3-methyl-1,5-pentanediol, 2,2-diethyl- 1,3-Propylene diol, 1,2-, 1,3- and 2,3-butanediol, etc.]]; and alcohols with rings [C8 or more and less than Mn600, for example, alicyclic-containing alcohols [1,4-bis]. (Hydroxymethyl) cyclohexane, etc.], aromatic aliphatic alcohols (m- and p-xylylene glycol, etc.)] and the like.
Of the above (a1), an aliphatic alcohol is preferable, an aliphatic alcohol having 2 to 4 carbon atoms is more preferable, and propylene glycol is particularly preferable.

Examples of the dicarboxylic acid (b1) include aliphatic [carbon numbers (hereinafter abbreviated as C) 3 to 30, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarbaryl acid]. Aromas [C8-30, eg phthalic acid, isophthalic acid, terephthalic acid, tetrabromphthalic acid,], and alicyclic-containing polycarboxylic acids [C6-50, eg 1,3-cyclobutanedicarboxylic acid, 1,3-cyclo Pentandicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane, dicyclohexyl-4,4'-dicarboxylic acid, dimer acid]; these polycarboxylic acids Estel-forming derivatives of [acid anhydride (maleic acid anhydride, phthalic acid anhydride, etc.), lower alkyl (C1-4) esters [dimethyl ester (dimethyl terephthalate, etc.), diethyl ester (diethyl maleate, etc.), etc.], acid Halide (terephthalic acid dichloride, etc.)] Dicarboxylic acid (b1) includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, orthophthalic acid, isophthalic acid, etc. Examples thereof include terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid.
Of the above (b1), aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and adipic acid and terephthalic acid are more preferable.

Examples of the tricarboxylic acid (b2) include (anhydrous) trimellitic acid.

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.
Further, in order for (A1) to satisfy the above conditions 1 and 2, for example, the following method can be mentioned.
(1) Adjust the degree of cross-linking according to (b2).
(2) Adjust the esterification rate.
(3) The weight ratio [(b2) / {(a1) + (b1)}] is preferably 0.5 / 100 to 2/100 for the esterification reaction.

<Polyurethane (A3)>
The polyurethane (A3) in the present invention comprises a polyester (A2) obtained by polycondensing a monomer containing a diol (a1) and a dicarboxylic acid (b1) as a constituent monomer, and a diisocyanate (c) as a constituent raw material. It is a polyurethane (A3) obtained by reacting the constituent raw materials contained in the above, and the 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 urethane group concentration can be appropriately adjusted depending on the type and weight of (c).

As for (a1) and (b1) in the polyester (A2), the same ones as those of the polyester (A1) can be mentioned, and the preferred ones are also the same.
Further, it is also preferable that the tricarboxylic acid (a2) is further made into a constituent monomer of (A2), as in the case of (A1).
Further, other matters are the same as those of the polyester (A1).

Examples of the diisocyanate (c) include (i) an aliphatic diisocyanate having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter) [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, etc. 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl -2,6-Diisocyanatohexanoate, 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 diisocyanate having 8 to 15 carbon atoms [m- and / or p-xylylene diisocyanate (XDI), α, α, α', α'-tetramethylxylylene diisocyanate (TMXDI), etc.]; Fragrance Specific examples of the group polyisocyanate include 1,3- and / or 1,4-phenylenediocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'-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 triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, etc .; (v) These diisocyanates Modified products (diisocyanate modified products having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.); and a mixture of two or more thereof.

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

Polyurethane (A3) can be produced, for example, by subjecting the polyester (A2) and diisocyanate (c) to a urethanization reaction.

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

<Molded product>
The molded product of the present invention is obtained by molding the resin composition (X). Further, a solution dissolved in a solvent may be applied and then the solvent may be removed.

The resin composition (X) and its molded product of the present invention are excellent in dilatancy when the resin (A) satisfies the conditions 1 and 2. Therefore, for example, it is considered that it can follow a slow deformation speed (high flexibility), becomes hard when an impact is applied, and can exhibit resin strength.
Therefore, it can be suitably used for various uses, adhesives, cushioning materials, vibration-proof materials, daily goods (for example, sports goods), medical goods and the like.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates weight% and parts indicate parts by weight. Further, Examples 1 to 3 shall be read as Reference Examples 1 to 3.

<Manufacturing example 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 640 parts of propylene glycol, 260 parts of terephthalic acid, 404 parts of adipic acid, 9.7 parts of trimellitic anhydride, and dibutyl tin oxide (DBTO) as a catalyst 2. Five parts were charged, and the temperature was raised to 180 ° C. over 3 hours while distilling off propylene glycol and water under aeration with nitrogen.
Next, the temperature was raised to 220 ° C. over 2 hours under a nitrogen atmosphere, and the reaction was continued at 220 ° C.
Further, when the acid value of the content became less than 10, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa. During the reaction under reduced pressure, return to normal pressure every 20 minutes to measure the molecular weight of the contents, reduce the pressure again, continue the reaction, and take out when the weight average molecular weight (Mw) reaches 53,000. A resin (polyester) (A-1) was obtained.

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

<Manufacturing example 7>
440 parts of resin (polyester) (A-1), 4.4 parts of isophorone diisocyanate (IPDI), and 1060 parts of N, N-dimethylformamide are charged in a pressure resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, and sealed. The reaction was carried out at 80 ° C. for 6 hours in this state to obtain a solution of a resin (polyurethane) (A-7) containing a hydroxy group at the terminal.
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>
In Production Example 7, a solution of each resin (polyurethane) (A) was obtained in the same manner as in Production Example 7 except according to Table 2. The results are shown in Table 2.

<Examples 1 to 3, Comparative Example 1>
The resins (A-4) to (A-6) and (ratio A-1) shown in Table 3 were used as they were to obtain each resin composition (X).
Each of the obtained resin compositions (X) was pressed with a heat press machine at 130 ° C. and 1 MPa to obtain a film having a thickness of 300 μm. The results are shown in Table 3.

<Examples 4 to 7, Comparative Example 2>
The solutions of the resins (A-7) to (A-10) and (ratio A-3) shown in Table 3 were used as they were to obtain each resin composition (X).
Each of the obtained resin compositions (X) was dried under a reduced pressure of 120 ° C. and then pressed with a heat press machine at 130 ° C. and 1 MPa to obtain a film having a thickness of 300 μm. 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 specific range in a low frequency region and a large frequency dependence of the storage elastic modulus as compared with the comparative one. be. From this, it is considered that the dilatancy is excellent, and the resin strength and flexibility (followability) are excellent.

The resin composition (X) of the present invention and a molded product thereof have excellent dilatancy, excellent flexibility, and (high followability), and further exhibit excellent resin strength when an impact is applied. Therefore, it is extremely useful because it can be suitably used for various uses, adhesives, cushioning materials, vibration-proof materials, daily products (for example, sports products), medical products, and the like.

Claims (1)

A film obtained by molding a resin composition (X) containing a resin (A) having a storage elastic acid (E') satisfying the following conditions 1 and 2 in dynamic viscoelasticity, wherein the resin (A) is used. A polyester (A2) obtained by polycondensing a monomer containing a diol (a1) and a dicarboxylic acid (b1) as a constituent monomer is reacted with a constituent raw material containing a diisocyanate (c) as a constituent raw material. A film obtained by molding a resin composition (X), which is a polyurethane (A3) and has a urethane group concentration of 0.1 to 10% by weight based on the weight of (A3).
<Condition 1>
Storage elastic modulus (E'1000) at vibration frequency 1000 Hz / storage elastic modulus (E'1) at 1 Hz is 20 or more <Condition 2>
Storage elastic modulus at vibration frequency 0.1 Hz (E'0.1) = 1 × 10 ⁵ to 1 × 10 ⁸ Pa