POLYESTER-BASED RESIN COMPOSITION

Abstract

The polyester-based resin composition according to the present invention is, at least, a polyester-based resin composition including: a polyester resin (A); a surfactant (B); and a terpene-based resin (C), in which the polyester resin (A) is obtained by copolymerizing, as a constituent component, a compound that has, as a frame, a polyalkylene glycol having a number of repeating units of from 3 to 50, in which the surfactant (B) is a non-ionic surfactant having a polyalkylene glycol frame, in which a mixing ratio (A)/(C) of the polyester resin (A) to the terpene-based resin (C) is from 80/20 to 99/1 by mass ratio, and in which the polyester-based resin composition has a water contact angle of 30 or less.

Claims

1. A polyester-based resin composition, comprising: a polyester resin (A); a surfactant (B); and a terpene-based resin (C), wherein the polyester resin (A) is obtained by copolymerizing, as a constituent component, a compound that has, as a frame, a polyalkylene glycol having a number of repeating units of from 3 to 50, wherein the surfactant (B) is a non-ionic surfactant having a polyalkylene glycol frame, wherein a mixing ratio (A)/(C) of the polyester resin (A) to the terpene-based resin (C) is from 80/20 to 99/1 by mass ratio, and wherein the polyester-based resin composition has a water contact angle of 30 or less.

2. The polyester-based resin composition according to claim 1, wherein the polyalkylene glycol in the compound that has, as a frame, a polyalkylene glycol having a number of repeating units of from 3 to 50 and that is a constituent component of the polyester resin (A), has a structure represented by Formula (1) or Formula (2) below:
HO((CH.sub.2).sub.aO).sub.bH (1)
HO(CH.sub.2CH((CH.sub.2).sub.cCH.sub.3)O).sub.dH (2) wherein, in Formula (1) and Formula (2), a represents a number from 2 to 4; c represents a number from 0 to 1, and each of b and d represents a number from 3 to 50.

3. The polyester-based resin composition according to claim 1, wherein a content of the polyalkylene glycol derived from the compound that has, as a frame, a polyalkylene glycol having a number of repeating units of from 3 to 50 and that is a constituent component of the polyester resin (A), is from 0.1 to 35% by mass.

4. The polyester-based resin composition according to claim 1, wherein the polyester resin (A) has a number average molecular weight of from 5,000 to 35,000.

5. The polyester-based resin composition according to claim 1, wherein the surfactant (B) has a structure represented by Formula (3) or Formula (4) below:
RO((CH.sub.2).sub.eO).sub.fH (3)
RO(CH.sub.2CH((CH.sub.2).sub.gCH.sub.3)O).sub.hH (4) wherein, in Formula (3) and Formula (4), each R represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cyclic ether group, or an aryl group; e represents a number from 2 to 4; g represents a number from 0 to 1; and each of f and h represents a number of 2 or more.

6. The polyester-based resin composition according to claim 1, wherein a content of the surfactant (B) is from 0.1 to 20% by mass.

7. The polyester-based resin composition according to claim 1, wherein the terpene-based resin (C) is an aromatic-modified terpene resin, a terpene phenol resin, or a hydrogenated product thereof.

8. The polyester-based resin composition according to claim 1, wherein the terpene-based resin (C) has a softening point of from 80 to 160 C.

9. An adhesive composition obtained by dissolving, in an organic solvent, the polyester-based resin composition according to claim 1.

Description

EXAMPLES

[0078] The present invention will now be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to these Examples.

[0079] 1. Evaluation Methods

[0080] 1-1. Contact Angle

[0081] The water contact angle was measured at 25 C., in accordance with a sessile drop method defined in JIS R 3257 (enacted on 1999). Type CA-X contact angle meter, manufactured by Kyowa Interface Science Co., Ltd., was used as a contact angle measuring apparatus.

[0082] 1-2. Number Average Molecular Weight

[0083] Apparatus: HLC-8220 GPC (manufactured by Tosoh Corporation)

[0084] Columns: Two TSKgel GMHXL columns (manufactured by Tosoh Corporation)

[0085] Column temperature: 40 C.

[0086] Eluent: Tetrahydrofuran, 1.00 mL/min

[0087] Detector: Differential refractometer (RI)

[0088] The molecular weight as measured by GPC is converted to a molecular weight in terms of polystyrene.

[0089] 1-3. Monomer Composition of Polyester Resin

[0090] An NMR measuring apparatus was used to measure .sup.1H-NMR, and the composition of the resin was determined from peak intensities of the respective copolymerization components. In the measurement, deuterated chloroform was used as a solvent for measurement.

[0091] 1-4. Melting Point, Glass Transition Point

[0092] A differential scanning calorimeter (DSC) was used for the measurement. The measurement was carried out at a temperature rise rate of 10 C./min.

[0093] 1-5. Stability Test of Adhesive Composition

[0094] A quantity of 70 g of the adhesive composition was added to a 100 mL glass bottle, and the bottle was sealed with a plug. After leaving the bottle to stand at 5 C. for 7 days, the adhesive composition was visually evaluated according to the following evaluation criteria.

[0095] A (Excellent): The adhesive composition remained in the form of a liquid.

[0096] B (Favorable): The adhesive composition solidified in an agar-like state, but returned to a liquid state at 25 C.

[0097] C (Inadequate): The adhesive composition solidified in an agar-like state, and did not return to a liquid state at 25 C.

[0098] 1-6. Peel Strength

(1) Preparation of Test Piece

[0099] The adhesive composition was coated, with a bar coater, on an aluminum foil (100 mm200 mm) having a thickness of 40 m. Thereafter, the resultant was dried at 100 C. for 3 minutes to remove the organic solvent contained in the adhesive composition, to form an adhesive layer having a film thickness of 30 m. Subsequently, a PET film having a thickness of 100 m was affixed on the surface of the adhesive layer, and a pressure was applied from the surface of the aluminum foil, using a thermal gradient tester, to press the film to the adhesive layer, thereby obtaining a test piece. The adhesion was carried out under the conditions of a temperature of 100 C., a pressure of 0.3 MPa, and a press time of 2 seconds.

(2) Measurement of T-peel Strength

[0100] The test piece was cut in a width of 10 mm, and the T-peel strength (N/10 mm) between the aluminum foil and the PET film was measured. The measurement was carried out under the conditions of a temperature of 25 C., and a tensile speed of 100 mm /min.

[0101] 2. Raw Materials

[0102] (1) Surfactants [0103] (S-1): Polyoxyethylene lauryl ether (EMULGEN 103, manufactured by Kao Corporation; HLB: 8.1) [0104] (S-2): Polyoxyethylene sorbitan monolaurate (LEODOL TW-L106, manufactured by Kao Corporation; HLB: 13.3) [0105] (S-3): Coconut amine acetate (ACETAMIN 24, manufactured by Kao Corporation) [0106] (S-4): Sodium dodecylbenzenesulfonate (NEOPELEX G-65, manufactured by Kao Corporation)

(2) Terpene-based Resins

[0107] (T-1): A terpene phenol resin (YS POLYSTER K140, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 140 C.) [0108] (T-2): A terpene phenol resin (YS POLYSTER K125, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 125 C.) [0109] (T-3): A terpene phenol resin (YS POLYSTER T160, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 160 C.) [0110] (T-4): A terpene phenol resin (YS POLYSTER T80, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 80 C.) [0111] (T-5): A terpene phenol resin (YS POLYSTER G150, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 150 C.) [0112] (T-6): A terpene resin (YS RESIN PX 1000, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 100 C.) [0113] (T-7): An aromatic-modified terpene resin (YS RESIN TO125, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 125 C.) [0114] (T-8): A hydrogenated product of an aromatic-modified terpene resin (CLEARON P115, manufactured by Yasuhara Chemical Co., Ltd.; softening point: 115 C.)

[0115] (Synthesis of Polyester Resin)

Synthesis Example 1

[0116] As shown in Table 1, 159 g of terephthalic acid, 52.9 g of isophthalic acid, 65.9 g of sebacic acid, 91.1 g of ethylene glycol, 92.5 g of 1,6-hexanediol, 39.1 g of PEG 200, and 0.3 g of tetrabutyl titanate as a polymerization catalyst were added into a reactor, and the atmosphere in the reactor was replaced with nitrogen. Then, the reactor was heated at 230 C. while stirring at 300 rpm, thereby allowing these raw materials to melt. After the temperature in the reactor reached 230 C., an esterification reaction was allowed to proceed for 3 hours. After a lapse of 3 hours, the temperature in the reactor was adjusted to 240 C., and the pressure in the reactor was reduced. After the pressure in the reactor reached a high vacuum (namely, a pressure of from 0.1 to 10.sup.5 Pa), a polymerization reaction was allowed to proceed for another 5 hours to obtain a polyester resin (P-1). The resulting polyester resin (P-1) had a number average molecular weight of 19,000, a melting point of 68 C., and a glass transition point of 3 C. The results are shown in Table 2. The content of the polyalkylene glycol was determined by NMR measurement of the resulting polyester resin.

TABLE-US-00001 TABLE 1 Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Example Raw Material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 10 Composition EG 91.1 94.0 93.6 87.3 84.3 81.5 86.9 86.4 85.8 94.1 of Added HG 92.5 119 115 59.1 32.1 6.9 105 107 107 119 Monomers PEG 200 39.1 0.3 6.7 87.6 127 163 (g) PEG 1000 43.5 PEG 2000 43.3 PEG 3000 46.1 TPA 159 164 163 152 147 142 151 150 149 164 IPA 52.9 54.6 54.3 50.7 48.9 47.3 50.4 50.1 49.8 54.6 SEA 65.9 68.1 67.7 63.2 61.1 59.0 62.9 62.6 62.1 68.1 Tetrabutyl 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 titanate

TABLE-US-00002 TABLE 2 Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Synthesis Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 10 Resin P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 P-10 Composition EG 20 20 20 20 20 20 20 20 20 20 (mol %) HG 24 30 29 16 9 2 29 29 30 30 PEG 200 6.0 0.05 1.0 14 21 28 PEG 1000 1.4 PEG 2000 0.7 PEG 3000 0.5 TPA 30 30 30 30 30 30 30 30 30 30 IPA 10 10 10 10 10 10 10 10 10 10 SEA 10 10 10 10 10 10 10 10 10 10 Polyalkylene Glycol 9.8 0.1 1.7 21 31 39 11 11 11 Content (% by mass) Number Average 19000 20000 19500 19000 20100 21000 20000 19000 19000 20000 Molecular Weight Melting Point ( C.) 68.0 70.0 68.0 72 60 58 68 68 68 70.0 Glass Transition 3.0 1.0 2.0 20 22 25 8 8 8 1.0 Point ( C.)

Synthesis Examples 2 to 10

[0117] Polycondensation reactions of polyester resins were carried out in the same manner as Synthesis Example 1, except that the monomers used and the composition of added monomers were changed as shown in Table 1. The respective physical property values of the resulting polyester resins are shown in Table 2.

[0118] The abbreviations used in Table 1, and in Table 2 to be described later, indicate those below. [0119] TPA: terephthalic acid [0120] IPA: isophthalic acid [0121] SEA: sebacic acid [0122] EG: ethylene glycol [0123] HG: 1,6-hexanediol [0124] PEG 200: polyethylene glycol (molecular weight: 200, number of repeating units: about 4.6) [0125] PEG 1000: polyethylene glycol (molecular weight: 1000, number of repeating units: about 23) [0126] PEG 2000: polyethylene glycol (molecular weight: 2000, number of repeating units: about 45) [0127] PEG 3000: polyethylene glycol (molecular weight: 3000, number of repeating units: about 68)

[0128] The final composition and characteristic values of each of the resulting polyester resins (P-1) to (P-10) are shown in Table 2.

Example 1

[0129] A quantity of 100 g of the polyester resin (P-1) synthesized in Synthesis Example 1, 0.1 g of the surfactant (S-1), 10 g of the terpene-based resin (T-1) were dissolved in 125 g of toluene and 125 g of methyl ethyl ketone, to obtain an adhesive composition having a solid content concentration of 31% by mass. Various properties of the resulting adhesive composition were evaluated. The results are shown in Table 3.

Examples 2 to 22 and Comparative Examples 1 to 6

[0130] Each of the adhesive compositions was obtained in the same manner as Example 1, except that the polyester resin, the surfactant, the terpene-based resin and the addition amount were changed as shown in Tables 3 and 4, and various properties thereof were evaluated. The results are shown in Tables 3, 4 and 5.

TABLE-US-00003 TABLE 3 Blend Composition (g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Polyester Synthesis 100 100 100 100 100 Resin Example 1 (P-1) Synthesis 100 Example 2 (P-2) Synthesis Example 3 (P-3) Synthesis Example 4 (P-4) Synthesis Example 5 (P-5) Synthesis Example 6 (P-6) Synthesis Example 7 (P-7) Synthesis Example 8 (P-8) Surfactant (S-1) 0.1 5.0 10 15 5.0 (S-2) 5.0 Terpene- (T-1) 10 10 10 10 10 10 based (T-2) Resin (T-3) (T-4) (T-5) (T-6) (T-7) (T-8) Organic Toluene 125 125 125 125 125 125 Solvent Methyl Ethyl 125 125 125 125 125 125 Ketone Appearance of Solution A A A A A A Contact Angle () 20 8 5 5 10 9 Peel Strength (N/10 mm) 30 28 24 16 28 26 Example Example Example Blend Composition (g) Example 7 Example 8 Example 9 10 11 12 Polyester Synthesis Resin Example 1 (P-1) Synthesis Example 2 (P-2) Synthesis 100 Example 3 (P-3) Synthesis 100 Example 4 (P-4) Synthesis 100 Example 5 (P-5) Synthesis 100 Example 6 (P-6) Synthesis 100 Example 7 (P-7) Synthesis 100 Example 8 (P-8) Surfactant (S-1) 5.0 5.0 5.0 5.0 5.0 5.0 (S-2) Terpene- (T-1) 10 10 10 10 10 10 based (T-2) Resin (T-3) (T-4) (T-5) (T-6) (T-7) (T-8) Organic Toluene 125 125 125 125 125 125 Solvent Methyl Ethyl 125 125 125 125 125 125 Ketone Appearance of Solution A A A A A A Contact Angle () 11 11 9 7 11 11 Peel Strength (N/10 mm) 25 29 27 16 29 27

TABLE-US-00004 TABLE 4 Example Example Example Example Example Example Example Example Example Example Blend Composition (g) 13 14 15 16 17 18 19 20 21 22 Polyester Synthesis 100 100 100 100 100 100 100 100 100 100 Resin Example 1 (P-1) Synthesis Example 2 (P-2) Synthesis Example 3 (P-3) Synthesis Example 4 (P-4) Synthesis Example 5 (P-5) Synthesis Example 6 (P-6) Synthesis Example 7 (P-7) Synthesis Example 8 (P-8) Surfactant (S-1) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (S-2) Terpene- (T-1) 5 15 25 based (T-2) 10 Resin (T-3) 10 (T-4) 10 (T-5) 10 (T-6) 10 (T-7) 10 (T-8) 10 Organic Toluene 125 125 125 125 125 125 125 125 125 125 Solvent Methyl Ethyl 125 125 125 125 125 125 125 125 125 125 Ketone Appearance of Solution A A A A A A A A A A Contact Angle () 7 20 30 7 6 10 8 12 11 7 Peel Strength (N/10 mm) 24 34 32 26 20 28 28 23 32 28

TABLE-US-00005 TABLE 5 Comparative Comparative Comparative Comparative Comparative Comparative Comparative Blend Composition (g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polyester Synthesis 100 100 100 100 100 Resin Example 1 (P-1) Synthesis 100 Example 9 (P-9) Synthesis 100 Example 10 (P-10) Surfactant (S-1) 5.0 5.0 15 (S-3) 5.0 (S-4) 5.0 Terpene-based (T-1) 10 10 10 10 40 10 Resin Organic Toluene 125 125 125 125 125 125 125 Solvent Methyl Ethyl 125 125 125 125 125 125 125 Ketone Appearance of Solution A A A A A A A Contact Angle () 65 78 4 5 5 67 75 Peel Strength (N/10 mm) 24 32 5 6 4 34 34

[0131] According to the results shown in Tables 3 and 4, the adhesive composition of each of Examples 1 to 22 had a water contact angle of 30 or less, and a high peel strength of 10 N/10 mm or more. It was found, from these results, that it was possible to obtain a polyester resin-based adhesive composition having both a favorable wettability to water and a favorable peel strength, and that the adhesive composition had a favorable solution stability.

[0132] The adhesive composition of Comparative Example 1 had a peel strength of 24 N/10 mm, which was favorable. However, the water contact angle of the composition was 65, since the surfactant and the terpene-based resin as recited in claim 1 were not contained therein.

[0133] The adhesive composition of Comparative Example 2 had a peel strength of 32 N/10 mm, which was favorable. However, the water contact angle of the composition was 78, since the surfactant contained therein was not a non-ionic surfactant having a polyalkylene glycol frame.

[0134] The adhesive composition of Comparative Example 3 had a water contact angle of 4. However, the peel strength of the composition was 5 N/10 mm, since the surfactant contained therein was not a non-ionic surfactant having a polyalkylene glycol frame.

[0135] The adhesive composition of Comparative Example 4 had a water contact angle 5. However, the peel strength of the composition was 6 N/10 mm, since the polyalkylene glycol copolymerized with the polyester resin had a number of repeating units above the range as recited in claim 1.

[0136] The adhesive composition of Comparative Example 5 had a water contact angle of 5. However, the peel strength of the composition was 4 N/10 mm, since no polyalkylene glycol was copolymerized with the polyester resin.

[0137] The adhesive composition of Comparative Example 6 had a peel strength of 34 N/10 mm. However, the water contact angle of the composition was 67, since the content of the terpene-based resin was too high.

[0138] The adhesive composition of Comparative Example 7 had a peel strength of 34N/10 mm, which was favorable. However, the water contact angle of the composition was 75, since the surfactant as recited in claim 1 was not contained therein.

INDUSTRIAL APPLICABILITY

[0139] The adhesive composition according to the present invention has properties of a polyester resin-based adhesive, and has excellent adhesiveness relative to a metal or resin material, as well as excellent mechanical properties. Further, the adhesive composition has a water contact angle of resin surface of 30 or less, and the portion of the resin surface which is exposed without being adhered maintains a favorable wettability to water. Such properties allow the adhesive composition to be preferably used as a hot melt adhesive having favorable ink transferability, for example, in a case of printing on a portion of an adhesive layer