ADHESIVE COMPOSITION

Abstract

A novel adhesive composition that exhibits excellent adhesiveness even to materials having poor adhesiveness, such as polyolefin materials. The adhesive composition includes a polymer having a partial structure represented by formula [I] (where R.sup.1 to R.sup.3 each independently represent an unsubstituted or substituted aryl group; R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, or R.sup.3 and R.sup.1 are optionally bonded by a single bond; A represents an unsubstituted or substituted arylene group; G represents a carbon atom, a silicon atom, or a germanium atom; and * represents a bonding position).

##STR00001##

Claims

1. An adhesive composition comprising a polymer having a partial structure represented by formula [I]: ##STR00014## (wherein R.sup.1 to R.sup.3 each independently represent an unsubstituted or substituted aryl group; R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, or R.sup.3 and R.sup.1 are optionally bonded by a single bond; A represents an unsubstituted or substituted arylene group, and G represents a carbon atom, a silicon atom, or a germanium atom; and * represents a bonding position).

2. The adhesive composition according to claim 1, wherein the polymer having the partial structure represented by formula [I] is a polymer having a repeating unit represented by formula [II]: ##STR00015## (wherein R.sup.1 to R.sup.3 each independently represent an unsubstituted or substituted aryl group; R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, or R.sup.3 and R.sup.1 are optionally bonded by a single bond; R.sup.4 represents a hydrogen atom or a methyl group, A represents an unsubstituted or substituted arylene group, G represents a carbon atom, a silicon atom, or a germanium atom, and X represents a single bond or a divalent linking group).

3. The adhesive composition according to claim 2, wherein the polymer having the repeating unit represented by formula [II] is a polymer consisting of one or more repeating units represented by formula [II].

4. The adhesive composition according to claim 1, wherein the adhesive composition is for a plastic material.

5. The adhesive composition according to claim 1, wherein the adhesive composition is for a polyolefin material.

6. A film formed with the adhesive composition according to claim 1.

7. The adhesive composition according to claim 2, wherein the adhesive composition is for a plastic material.

8. The adhesive composition according to claim 3, wherein the adhesive composition is for a plastic material.

9. The adhesive composition according to claim 2, wherein the adhesive composition is for a polyolefin material.

10. The adhesive composition according to claim 3, wherein the adhesive composition is for a polyolefin material.

11. A film formed with the adhesive composition according to claim 2.

12. A film formed with the adhesive composition according to claim 3.

13. A film formed with the adhesive composition according to claim 4.

14. A film formed with the adhesive composition according to claim 5.

15. A film formed with the adhesive composition according to claim 7.

16. A film formed with the adhesive composition according to claim 8.

17. A film formed with the adhesive composition according to claim 9.

18. A film formed with the adhesive composition according to claim 10.

Description

EXAMPLES

Synthesis Example 1

1) Synthesis of 2-(4-Tritylphenoxy)ethyl methacrylate

[0095] ##STR00013##

[0096] 2-(4-Tritylphenoxy)ethanol (100 g, 0.26 mol) and toluene (1.5 L) were added to a 3 L four-necked flask purged with nitrogen. The mixture was stirred at room temperature for 15 min, and then methacrylic acid (27.25 g, 0.31 mol) and p-toluenesulfonic acid (25.02 g, 0.13 mol) were added. The reaction solution was heated to 110-120 C. and stirred for 9 h. Then, the reaction solution was cooled to room temperature. Ethyl acetate (0.5 L) was added to the reaction solution, and the mixture was water-washed twice with distilled water. The organic layer was dehydrated with anhydrous magnesium sulfate, and then the solvent was distilled off by an evaporator. The obtained crude product was recrystallized with ethanol to obtain 2-(4-tritylphenoxy) ethyl methacrylate (81.00 g, yield 68.70%).

[0097] .sup.1H NMR (500 MHz, Chloroform-d.sub.1, TMS) /ppm=1.95 (s, 3H), 4.20 (t, 2H), 4.48 (t, 2H), 5.58 (s, 1H), 6.14 (s, 1H), 6.81 (m, 2H), 7.13-7.22 (m, 19H).

[0098] .sup.13C NMR (125 MHz, Chloroform-d.sub.1) /ppm=18.3, 63.3, 64.4, 65.9, 113.5, 126.0, 127.6, 131.3, 132.4, 136.0, 139.6, 147.0, 156.6, 167.4.

[0099] HR-MS (TOF MS ESI, pos): 471.1909 M+Na.sup.+ (calculated: 471.1931).

2) Synthesis of Poly(2-(4-tritylphenoxy)ethyl methacrylate)

[0100] The polymer was made by a thermal radical polymerization reaction using azobisisobutyronitrile (AIBN) as an initiator. 2-(4-Tritylphenoxy)ethyl methacrylate and AIBN were added to a 100 mL Schlenk tube. A stirring bar was placed, and the Schlenk tube was sealed with a three-way cock, and then a gas sampling bag containing nitrogen was mounted. The gas in the reaction vessel was degassed by a vacuum pump to be changed into nitrogen. Then, 25 mL of deoxygenated toluene was added, and the mixture was heated and stirred in an oil bath at 65 C. for 24 h for a radical polymerization reaction. After the completion of the reaction, the target poly{2-(4-tritylphenoxy)ethyl methacrylate} (polymers A to E) were obtained by reprecipitation with hexane.

[0101] The number average molecular weights of the polymers A to E were adjusted by monomer (M)/AIBN ratios. The monomer (M)/AIBN ratios in the polymers, the amounts of the reagents corresponding to the ratios used, and the number average molecular weights (Mn) and molecular weight distributions (Mw/Mn) of each of the synthesized polymers are shown in Table 1.

TABLE-US-00001 TABLE 1 Polymerization Conditions and Molecular Weight Characteristics of Polymers A to E [M]/[AIBN] Monomer (g) AIBN (g) Mn (10.sup.3) Mw/Mn A 100/1 10.0 0.0366 23.7 2.04 B 200/1 10.0 0.0183 41.5 2.24 C 400/1 10.0 0.0092 58.9 1.90 D 800/1 10.0 0.0046 79.8 1.73 E 1000/1 10.0 0.0037 88.8 1.68

[0102] The GPC measurement conditions used for the analysis of the polymers (A to E) are shown below.

[0103] [Apparatuses]

Sample injection apparatus: Waters 2695 Alliance
Separation columns: Shodex SB-G, SB-806HQ, SB-805HQ, SB-804HQ, and SB-803HQ
Detectors: Waters 2414 differential refractive index (RI) detector and 2998 photodiode array (PDA) detector
Column oven: column oven manufactured by Waters Corporation

[0104] [Conditions]

Column oven: 40 C.
RI detector temperature: 40 C.
Mobile phase: DMF
Flow rate: 1.0 mL/min
Standard injected amount: 200 L
PDA detector extracted wave: 254.0 nm
Quantitative calculation: standard poly(methyl methacrylate) conversion

Example 1

[0105] (Making of Adhesive Compositions)

[0106] Each of the synthesized polymers (A to E) (1.0 g) was dissolved in cyclohexanone (99.0 g) by heating to obtain adhesive compositions A to E having a solid concentration of 1 wt %.

[0107] (Making of Coating Films)

[0108] The adhesive compositions A to E made were formed into films on various substrates having a size of 5050 mm by a bar coating method so as to be roughly 300 nm thickness, thereby obtaining coating films A to E. The heating conditions were drying at 80 C. for 5 min.

[0109] The substrates used are shown below.

ZEONOR Film ZF-16 (manufactured by ZEON Corporation, cycloolefin polymer (COP), 188 m)
ZEONEX 790R (manufactured by ZEON Corporation, COP, 2 mm) APEL 6015T (manufactured by Mitsui Chemicals, Inc., cycloolefin copolymer (COC), 2 mm)

[0110] (Evaluation of Adhesiveness)

[0111] The adhesiveness between the coating films and the polyolefin substrates was evaluated by the cross-cut tape peeling test in former JIS K5400. 11 vertical cuts and 11 horizontal cuts at intervals of 1 mm were made in each of the coating films A to E to make 100 squares. CELLOTAPE (registered trademark) was stuck and adhered to each sample by rubbing a plurality of times with the inner surface of a finger, and then the tape was peeled. Evaluation was performed by the remaining number of squares of the grid on the coating film without peeling. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Results of Cross-Cut Tape Peeling Test Polyolefin substrates ZEONOR Film Coating film ZF-16 ZEONEX790R APEL6015T A 28/100 43/100 100/100 B 40/100 37/100 100/100 C 100/100 100/100 100/100 D 100/100 100/100 100/100 E 100/100 100/100 100/100

[0112] In Table 2, the numbers of the numerators represent the remaining number of squares of the grid on the coating film without peeling.

Synthesis Example 2

Synthesis of Random Copolymer with 2-(4-Tritylphenoxy) ethyl methacrylate/Butyl methacrylate=75/25 (Molar Ratio)

[0113] 7.51 g (16.74 mmol) of 2-(4-tritylphenoxy)ethyl methacrylate (monomer), 0.0094 g (0.06 mmol) of AIBN (product of TOKYO CHEMICAL INDUSTRY, recrystallized product), 17.80 g of toluene (Wako Pure Chemical Industries, deoxygenated grade), and 0.87 g (6.12 mmol) of butyl methacrylate (monomer) (MITSUBISHI RAYON) were added to a 50 mL two-necked flask equipped with a magnetic stirring bar, a septum rubber, a three-way cock, and a nitrogen balloon, and dissolved. Then, the gas in the flask was degassed under reduced pressure, and the solution was heated and stirred in an oil bath at 80 C. After 26 h, the heating and stirring was stopped, and the reaction solution was dropped into 800 mL of hexane to be powdered. The obtained precipitate was filtered, and dried under reduced pressure to obtain 8.77 g of a polymer F. As a result of GPC measurement, the polymer F had a number average molecular weight (Mn) of 55.510.sup.3, a weight average molecular weight (Mw) of 15310.sup.3, and a molecular weight distribution (Mw/Mn) of 2.75.

[0114] The GPC measurement conditions used for the analysis of the polymer F are shown below.

[0115] [Apparatuses]

Sample injection apparatus: 2695 Alliance manufactured by Waters Corporation
Separation columns: Shodex KF-805 L, KF-804 L, and KF-804 L
Detectors: 2414 differential refractive index (RI) detector manufactured by Waters Corporation
Column oven: column oven manufactured by Waters Corporation

[0116] [Conditions]

Column oven: 40 C.
RI detector temperature: 40 C.
Mobile phase: tetrahydrofuran
Flow rate: 1.0 mL/min
Standard injected amount: 100 L
Quantitative calculation: standard polymethyl methacrylate conversion

Example 2

[0117] (Making of Adhesive Composition)

[0118] The synthesized polymer F (0.1 g) was dissolved in cyclohexanone (9.9 g) by heating to obtain an adhesive composition F having a solid concentration of 1 wt %.

[0119] (Making of Coating Film)

[0120] A coating film F was obtained by coating the adhesive composition F made on APEL 6015T (manufactured by Mitsui Chemicals, Inc., cycloolefin copolymer (COC), 2 mm) having a size of 5050 mm with a bar coating method so as to be roughly 300 nm thickness. The coated substrate was dried in an oven (120 C., 5 min) to obtain a molded body.

[0121] (Evaluation of Adhesiveness)

[0122] The adhesiveness between the coating film F and the COC substrate was evaluated by the cross-cut tape peeling test in former JIS K5400. The result of the test was 100/100.