TWO-COMPONENT ADHESIVE COMPOSITION

Abstract

An adhesive composition is provided and includes the following components (A) to (D): (A) a radically polymerizable compound; (B) (B-1) a polymer consisting of at least one repeat unit derived from a polymerizable compound of formula (I), or (B-2) a polymer consisting of at least one repeat unit derived from a polymerizable compound of formula (I), and at least one repeat unit derived from another radically polymerizable compound; (C) a polymerization initiator; and (D) a reducing agent.

##STR00001##

Claims

1. An adhesive composition comprising the following components (A) to (D): (A) a radically polymerizable compound; (B) (B-1) a polymer consisting of at least one repeat unit derived from a polymerizable compound of formula (I), or (B-2) a polymer consisting of at least one repeat unit derived from a polymerizable compound of formula (I), and at least one repeat unit derived from another radically polymerizable compound: ##STR00008## (wherein X.sup.1 and X.sup.2 each independently represent a C7 to C20 alkyl group or a C7 to C20 alkoxy group, n represents 0 or 1, Z.sup.1 and Z.sup.2 each independently represent a single bond or a C1 to C3 alkylene group, each R independently represents an organic group or a halogeno group, m1 and m2 each independently represent any integer of 0 to 4, and Y represents a polymerizable functional group); (C) a polymerization initiator; and (D) a reducing agent.

2. The adhesive composition according to claim 1, wherein the polymerization initiator is cumene hydroperoxide.

3. The adhesive composition according to claim 1, wherein the reducing agent is at least one compound selected from the group consisting of vanadyl acetylacetonate, cobalt octylate, cobalt naphthenate and ethylenethiourea.

4. The adhesive composition according to claim 1, wherein the adhesive composition further comprises polybutadiene.

5. The adhesive composition according to claim 1, wherein the adhesive composition consists of a mixture of a first agent containing at least the component (C) and a second agent containing at least the component (D).

6. A compact obtained by applying the adhesive composition according to claim 1 onto a plastic base material, and curing the adhesive composition so that the resulting layer is disposed on the base material or between base materials.

Description

EXAMPLES

[0125] The number-average molecular weights of polymers obtained in Examples were measured using the following apparatus and conditions.

Apparatus

[0126] Sample injection apparatus: Waters 2695 Alliance
Separation column: Shodex KF-G, 805L, 804L, and 804L
Detector: Waters 2414 differential refractive index (RI) detector and 2998 photodiode array (PDA) detector
Column oven: Column oven manufactured by Waters Corp.

Conditions

[0127] Column oven temperature: 40° C.
RI detector temperature: 40° C.
Mobile phase: Tetrahydrofuran
Flow rate: 1.0 mL/min
Standard injection volume: 200 μL
PDA detector extraction wave: 254.0 nm
Quantitative calculation: Based on standard polymethyl methacrylate

Synthesis Example 1

Synthesis of N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl) acrylamide (DOPAA)

[0128] ##STR00007##

[0129] To a 1 L four-neck flask purged with nitrogen, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]amine (50.00 g, 0.127 mol), N,N-dimethylaniline (46.17 g, 0.381 mol), and 477 mL of super dehydrated dichloromethane were added, and stirred until uniformly dissolved. Subsequently, the reaction solution was cooled to 0° C. or lower in an ice/ethanol bath, and acrylic acid chloride (22.99 g, 0.254 mol) was slowly added dropwise thereto, followed by stirring for 30 minutes. Then, the reaction solution was warmed to room temperature and reacted for 24 hours. After the completion of reaction, the solvent was distilled off with an evaporator, and the crude product was dissolved in 250 mL of ethyl acetate. Then, the solution was washed with a 1 N aqueous hydrochloric acid solution, a saturated aqueous solution of sodium bicarbonate, and saline. The organic layer was dehydrated over magnesium sulfate, and the filtrate was then distilled off with an evaporator. The obtained crude product was recrystallized and purified with hexane to obtain N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide (38.67 g, percent yield: 68%). Results of mass spectrometry will be shown below. High Resolution ESI-TOF-MS m/z Calcd. for [C.sub.31H.sub.45NO ([M+Na].sup.+)]: 470.3393 found 470.3317.

Synthesis Example 2

Production of Adhesive Polymer 1 (DOPAA/EA=90/10)

[0130] To a 300 mL four-neck flask, 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=28.19 g, Mn=17,379, Mw/Mn=2.08

Synthesis Example 3

Production of Adhesive Polymer 2 (DOPAA/EA=90/10)

[0131] To a 300 mL four-neck flask, 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 40.62 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=27.82 g, Mn=26,399, Mw/Mn=2.20

Synthesis Example 4

Production of Adhesive Polymer 3 (DOPAA/EA=90/10)

[0132] To a 300 mL four-neck flask, 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 36.69 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=29.01 g, Mn=29,109, Mw/Mn=2.10

Synthesis Example 5

Production of Adhesive Polymer 4 (DOPAA/EA=90/10)

[0133] To a 300 mL four-neck flask, 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 33.18 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=28.87 g, Mn=31,641, Mw/Mn=2.20

Synthesis Example 6

Production of Adhesive Polymer 5 (DOPAA/EA=90/10)

[0134] To a 300 mL four-neck flask, 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 30.02 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=27.31 g, Mn=34,687, Mw/Mn=2.38

Synthesis Example 7

Production of Adhesive Polymer 6 (DOPAA/EA=90/10)

[0135] To a 300 mL four-neck flask, 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 20.02 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=28.11 g, Mn=36,941, Mw/Mn=2.94

Synthesis Example 8

Production of Adhesive Polymer 7 (DOPAA/EA=85/15)

[0136] To a 300 mL four-neck flask, 25.52 g of DOPAA, 4.50 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45.03 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=29.33 g, Mn=21,484, Mw/Mn=2.11

Synthesis Example 9

Production of Adhesive Polymer 8 (DOPAA/EA=80/20)

[0137] To a 300 mL four-neck flask, 24.02 g of DOPAA, 6.00 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45.03 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=28.13 g, Mn=24,577, Mw/Mn=1.98

Synthesis Example 10

Production of Adhesive Polymer 9 (DOPAA/EA=70/30)

[0138] To a 300 mL four-neck flask, 21.01 g of DOPAA, 9.00 g of ethyl acrylate (EA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45.03 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=28.83 g, Mn=19,320, Mw/Mn=2.18

Synthesis Example 11

Production of Adhesive Polymer 10 (DOPAA/MA=90/10)

[0139] To a 300 mL four-neck flask, 18.10 g of DOPAA, 2.00 g of methyl acrylate (MA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.14 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 30 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.07 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=16.23 g, Mn=13,360, Mw/Mn=1.84

Synthesis Example 12

Production of Adhesive Polymer 11 (DOPAA/nBA=90/10)

[0140] To a 300 mL four-neck flask, 18.09 g of DOPAA, 2.10 g of n-butyl acrylate (nBA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.18 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 30 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.09 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=17.93 g, Mn=15,615, Mw/Mn=1.71

Synthesis Example 13

Production of Adhesive Polymer 12 (DOPAA/iBA=90/10)

[0141] To a 300 mL four-neck flask, 18.09 g of DOPAA, 2.10 g of i-butyl acrylate (iBA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.18 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 30 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.09 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=18.03 g, Mn=16,271, Mw/Mn=1.88

Synthesis Example 14

Production of Adhesive Polymer 13 (DOPAA/THFA=90/10)

[0142] To a 300 mL four-neck flask, 26.97 g of N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide (DOPAA), 2.99 g of tetrahydrofurfuryl acrylate (THFA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=27.23 g, Mn=13,901, Mw/Mn=2.21

Synthesis Example 15

Production of Adhesive Polymer 14 (DOPAA/HEA=90/10)

[0143] To a 300 mL four-neck flask, 27.10 g of DOPAA, 3.03 g of 2-hydroxyethyl acrylate (HEA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=27.15 g, Mn=22,703, Mw/Mn=2.29

Synthesis Example 16

Production of Adhesive Polymer 15 (DOPAA/EHA=90/10)

[0144] To a 300 mL four-neck flask, 27.03 g of DOPAA, 3.02 g of 2-ethylhexyl acrylate (EHA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 45 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=26.90 g, Mn=12,588, Mw/Mn=1.80

Synthesis Example 17

Production of Adhesive Polymer 16 (DOPAA/styrene=90/10)

[0145] To a 300 mL four-neck flask, 30.00 g of DOPAA, 3.33 g of styrene (a product of Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 50 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=31.60 g, Mn=22,408, Mw/Mn=2.36

Synthesis Example 18

Production of Adhesive Polymer 17 (DOPAA/DEAA=90/10)

[0146] To a 300 mL four-neck flask, 30.00 g of DOPAA, 3.33 g of N,N-diethylacrylamide (DEAA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.19 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 50 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=30.00 g, Mn=25,377, Mw/Mn=2.08

Synthesis Example 19

Production of Adhesive Polymer 18 (DOPAA/maleic anhydride=90/10)

[0147] To a 300 mL four-neck flask, 20.00 g of DOPAA, 2.22 g of maleic anhydride (a product of Tokyo Chemical Industry Co., Ltd.), and 0.14 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 22.2 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=20.07 g, Mn=28,576, Mw/Mn=1.78

Synthesis Example 20

Production of Adhesive Polymer 19 (DOPAA/iBMA=90/10)

[0148] To a 300 mL four-neck flask, 20.00 g of DOPAA, 2.22 g of isobutyl methacrylate (iBMA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.13 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 22.2 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=21.11 g, Mn=26,758, Mw/Mn=2.33

Synthesis Example 21

Production of Adhesive Polymer 20 (DOPAA/EHMA=90/10)

[0149] To a 300 mL four-neck flask, 20.00 g of DOPAA, 2.22 g of 2-ethylhexyl methacrylate (EHMA: a product of Tokyo Chemical Industry Co., Ltd.), and 0.12 g of AIBN (a product of Tokyo Chemical Industry Co., Ltd.) were added, and dissolved in 22.2 g of toluene. Deaeration was performed by the application of pressure reduction operation, and the mixture was heated and stirred at 65° C. for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added thereto, and the mixture was stirred at 80° C. for 5 hours. While heating and stirring were terminated, the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was added dropwise into 800 mL of methanol for powdering. The obtained precipitates were filtered off and dried under reduced pressure at 60° C. in a vacuum dryer. Yield=21.38 g, Mn=35,929, Mw/Mn=1.90

Synthesis Example 22

Production of Adhesive Polymer 21 (poly{N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide} (PDOPAA))

[0150] To a 500 mL four-neck flask, 100.0 g of DOPAA, 150.0 g of toluene, and 0.322 g of AIBN were added, and warmed to 30° C. in a nitrogen atmosphere. After confirmation that the inside of the system was homogeneous, deaeration under reduced pressure was performed three times with a diaphragm pump while the mixture was stirred with a magnetic stirrer. The mixture thus deaerated was warmed to 65° C. and stirred for 24 hours. Then, the flask was brought back to room temperature, and reprecipitation was performed using 1600 mL of methanol. A white powder was obtained by vacuum drying at 120° C. for 2 hours. Yield=96.00 g, Mn=14,315, Mw/Mn=1.89

Preparation of Adhesive Composition

[0151] The respective components in the amounts shown in Tables 1 to 11 were stirred and mixed to obtain adhesive compositions. The composition obtained using cumene hydroperoxide (2) was used as the first agent, and the composition obtained using vanadyl acetylacetonate (3) was used as the second agent. Equal amounts of the first agent and the second agent were stirred and mixed to obtain an adhesive composition.

[0152] In Tables 1 to 11, the amount of each substance mixed is indicated by parts by mass. The details of each mixed substance are as described below.

EHMA: 2-Ethylhexyl methacrylate, a commercially available product
MMA: Methyl methacrylate, a commercially available product
EMA: Ethyl methacrylate, a commercially available product
nBMA: n-Butyl methacrylate, a commercially available product
iBMA: i-Butyl methacrylate, a commercially available product
CHMA: Cyclohexyl methacrylate, a commercially available product
IBOMA: Isobornyl methacrylate, a commercially available product
LMA: Lauryl methacrylate, a commercially available product
BzMA: Benzyl methacrylate, a commercially available product
THFMA: Tetrahydrofurfuryl methacrylate, a commercially available product
Cumene hydroperoxide: a commercially available product
Vanadyl acetylacetonate: a commercially available product
Cobalt octylate: a commercially available product
Cobalt naphthenate: a commercially available product
Ethylenethiourea: a commercially available product
NBR: Acrylonitrile-butadiene rubber, a commercially available product
SBR: Styrene-butadiene rubber, a commercially available product
Bis-GMA: 2,2-Bis[4(-hydroxy-3-methacryloyloxypropoxy)phenyl]propane, a commercially available product
TE-2000: Nippon Soda Co., Ltd., terminally urethane methacrylate-modified polybutadiene
TEAI-1000: Nippon Soda Co., Ltd., terminally urethane acrylate-modified polybutadiene

Tensile Shear Strength (Tensile Shear Adhesive Strength)

[0153] The following test pieces were used.

[0154] Examples 1 to 40 and Comparative Examples 1 to 4: Polypropylene (PP)

[0155] Example 41: High-density polyethylene (HDPE)

[0156] Example 42: Low-density polyethylene (LDPE)

[0157] Example 43: Cycloolefin polymer (COP)

[0158] Example 44: Cycloolefin copolymer (COC)

[0159] Example 45: Polymethylpentene (PMP)

[0160] Examples 46 and 61: Polytetrafluoroethylene (PTFE)

[0161] Example 47: Polydimethylsilicone (PDMS)

[0162] Example 48: Polycarbonate (PC)

[0163] Example 49: Polystyrene (PS)

[0164] Example 50: Polymethyl methacrylate (PMMA)

[0165] Example 51: Polyethylene terephthalate (PET)

[0166] Example 52: Hard polyvinyl chloride (PVC)

[0167] Example 53: Nylon 6 (PA6)

[0168] Example 54: Polyacetal (POM)

[0169] Example 55: Polyether ether ketone (PEEK)

[0170] Example 56: Liquid crystal polyester (LCP)

[0171] Example 57: Polyphenylene sulfide (PPS)

[0172] Example 58: Modified polyphenylene ether (m-PPE)

[0173] Example 59: Polybutylene terephthalate (PBT)

[0174] Example 60: Acrylonitrile-butadiene-styrene (ABS)

[0175] All adherend substrates used had a size of 100×25×2.0 mm. Each adherend was used after being wiped with waste cloth. The adhesive composition of the first agent and the second agent mixed with each other was applied to one side of one sheet of each test piece in accordance with JISK-6850 in an environment involving a temperature of 23° C. and a humidity of 50%, and the test piece was immediately bonded to another sheet of the test piece. The thickness of the adhesive agent layer was 0.1 mm. Then, the resultant was cured at room temperature for 24 hours, used as a sample for tensile shear strength measurement, and subjected to the measurement of tensile shear strength (unit: MPa) to determine tensile shear strength. The measurement was performed at a pulling speed of 10 mm/min in an environment involving a temperature of 23° C.

TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example Example Reagent 1 2 3 4 5 6 7 8 First agent (A) EHMA 100 100 100 100 100 100 100 100 (B) Adhesive polymer 1 15 Adhesive polymer 2 15 Adhesive polymer 3 15 Adhesive polymer 4 15 Adhesive polymer 5 15 Adhesive polymer 6 15 Adhesive polymer 7 15 Adhesive polymer 8 15 (C) Cumene 5 5 5 5 5 5 5 5 hydroperoxide Second (A) EHMA 100 100 100 100 100 100 100 100 agent (B) Adhesive polymer 1 15 Adhesive polymer 2 15 Adhesive polymer 3 15 Adhesive polymer 4 15 Adhesive polymer 5 15 Adhesive polymer 6 15 Adhesive polymer 7 15 Adhesive polymer 8 15 (D) Vanadyl 1 1 1 1 1 1 1 1 acetylacetonate Evaluation Adherend PP PP PP PP PP PP PP PP Tensile shear adhesive 1.11 1.22 2.44 2.35 1.37 1.40 1.74 1.84 strength/MPa Fracture mechanism Interface Interface Material Interface Interface Interface Interface Interface fracture

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example Example Reagent 9 10 11 12 13 14 15 16 First (A) EHMA 100 100 100 100 100 100 100 100 agent (B) Adhesive polymer 9 15 Adhesive polymer 10 15 Adhesive polymer 11 15 Adhesive polymer 12 15 Adhesive polymer 13 15 Adhesive polymer 14 15 Adhesive polymer 15 15 Adhesive polymer 16 15 (C) Cumene 5 5 5 5 5 5 5 5 hydroperoxide Second (A) EHMA 100 100 100 100 100 100 100 100 agent (B) Adhesive polymer 9 15 Adhesive polymer 10 15 Adhesive polymer 11 15 Adhesive polymer 12 15 Adhesive polymer 13 15 Adhesive polymer 14 15 Adhesive polymer 15 15 Adhesive polymer 16 15 (D) Vanadyl 1 1 1 1 1 1 1 1 acetylacetonate Evaluation Adherend PP PP PP PP PP PP PP PP Tensile shear adhesive 1.17 1.54 1.63 1.38 1.51 1.33 1.28 1.74 strength/MPa Fracture mechanism Interface Interface Interface Interface Interface Interface Interface Interface

TABLE-US-00003 TABLE 3 Example Example Example Example Example Reagent 17 18 19 20 21 First (A) )EHMA 100 100 100 100 100 agent (B) Adhesive polymer 17 15 Adhesive polymer 18 15 Adhesive polymer 19 15 Adhesive polymer 20 15 Adhesive polymer 21 15 (C) Cumene hydroperoxide 5 5 5 5 5 Second (A) EHMA 100 100 100 100 100 agent (B) Adhesive polymer 17 15 Adhesive polymer 18 15 Adhesive polymer 19 15 Adhesive polymer 20 15 Adhesive polymer 21 15 (D) Vanadyl 1 1 1 1 1 acetylacetonate Evaluation Adherend PP PP PP PP PP Tensile shear adhesive 1.44 2.07 1.94 1.11 strength/MPa Fracture mechanism Interface Interface Interface Interface Interface

TABLE-US-00004 TABLE 4 Example Example Example Example Reagent 22 23 24 25 First agent (A) MMA 100 100 100 100 (B) Adhesive polymer 3 15 10 10 10 (C) Cumene hydroperoxide 5 5 5 5 Second agent (A) MMA 100 (B) Adhesive polymer 3 15 10 10 10 (D) Vanadyl acetylacetonate 1 Cobalt octylate 1 Cobalt naphthenate 1 Ethylenethiourea 1 Evaluation Adherend PP PP PP PP Tensile shear 1.12 0.65 0.38 1.02 adhesive strength/MPa Fracture mechanism Interface Interface Interface Interface

TABLE-US-00005 TABLE 5 Example Example Example Example Example Example Example Example Example Reagent 26 27 28 29 30 31 32 33 34 First (A) EMA 100 agent nBMA 100 iBMA 100 50 CHMA 100 IBOMA 100 LMA 100 50 BzMA 100 THFMA 100 (B) Adhesive 15 15 15 15 15 15 15 15 15 polymer 3 (C) Cumene 5 5 5 5 5 5 5 5 5 hydroperoxide Second (A) EMA 100 agent nBMA 100 iBMA 100 50 CHMA 100 IBOMA 100 LMA 100 50 BzMA 100 THFMA 100 (B) Adhesive 15 15 15 15 15 15 15 15 15 polymer 3 (D) Vanadyl 1 1 1 1 1 1 1 1 1 acetylacetonate Evaluation Adherend PP PP PP PP PP PP PP PP PP Tensile shear 0.78 0.98 0.61 0.45 0.37 0.76 0.55 1.06 1.58 adhesive strength/MPa Fracture Interface Interface Interface Interface Interface Interface Interface Interface Interface mechanism

TABLE-US-00006 TABLE 6 Example Example Example Example Example Example Reagent 35 36 37 38 39 40 First (A) MMA 100 100 agent EHMA 100 100 100 100 (B) Adhesive polymer 3 10 15 15 15 15 10 (C) Cumene hydroperoxide 5 5 5 5 5 5 (Others) NBR 15 10 SBR 10 10 Bis-GMA 5 TE-2000 5 TEAI-1000 5 Second (A) MMA 100 100 agent EHMA 100 100 100 100 (B) Adhesive polymer 3 10 15 15 15 15 10 (D) Vanadyl acetylacetonate 5 5 5 5 5 5 (Others) NBR 15 10 SBR 10 10 Bis-GMA 5 TE-2000 5 TEAI-1000 5 Evaluation Adherend PP PP PP PP PP PP Tensile shear adhesive 1.33 2.39 1.65 1.69 2.22 1.28 strength/MPa Fracture mechanism Interface Material Interface Interface Interface Interface fracture

TABLE-US-00007 TABLE 7 Example Example Example Example Example Example Example Example Example Reagent 41 42 43 44 45 46 47 48 49 First (A) EHMA 100 100 100 100 100 100 100 100 100 agent (B) Adhesive 15 15 15 15 15 15 15 15 15 polymer 3 (C) Cumene 5 5 5 5 5 5 5 5 5 hydroperoxide Second (A) EHMA 100 100 100 100 100 100 100 100 100 agent (B) Adhesive 15 15 15 15 15 15 15 15 15 polymer 3 (D) Vanadyl 1 1 1 1 1 1 1 1 1 acetylacetonate Evaluation Adherend HDPE LDPE COP COC PMP PTFE PDMS PC PS Tensile shear 1.69 1.33 2.89 3.78 2.34 1.09 0.55 3.11 1.58 adhesive strength/MPa Fracture Material Material Interface Interface Interface Material Material Interface Material mechanism fracture fracture fracture fracture fracture

TABLE-US-00008 TABLE 8 Example Example Example Example Example Example Example Example Example Reagent 50 51 52 53 54 55 56 57 58 First (A) EHMA 100 100 100 100 100 100 100 100 100 agent (B) Adhesive 15 15 15 15 15 15 15 15 15 polymer 3 (C) Cumene 5 5 5 5 5 5 5 5 5 hydroperoxide Second (A) EHMA 100 100 100 100 100 100 100 100 100 agent (B) Adhesive 15 15 15 15 15 15 15 15 15 polymer 3 (D) Vanadyl 1 1 1 1 1 1 1 1 1 acetylacetonate Evaluation Adherend PMMA PET PVC PA6 POM PEEK LCP PPS m-PPE Tensile shear 3.47 3.07 2.09 2.87 2.11 2.88 2.27 3.26 3.78 adhesive strength/MPa Fracture Interface Interface Interface Interface Interface Interface Material Interface Interface mechanism fracture

TABLE-US-00009 TABLE 9 Example Example Reagent 59 60 First agent (A) EHMA 100 100 (B) Adhesive polymer 3 15 15 (C) Cumene hydroperoxide 5 5 Second agent (A) EHMA 100 100 (B) Adhesive polymer 3 15 15 (D) Vanadyl acetylacetonate 1 1 Evaluation Adherend PBT ABS Tensile shear 2.76 4.02 adhesive strength/MPa Fracture mechanism Interface Interface

TABLE-US-00010 TABLE 10 Comparative Comparative Comparative Comparative Reagent Example 1 Example 2 Example 3 Example 4 First agent (A) EHMA 100 MMA 100 THFMA 100 BzMA 100 (C) Cumene hydroperoxide 5 5 5 5 (Others) SBR 10 NBR 15 15 15 Second agent (A) EHMA 100 MMA 100 THFMA 100 BzMA 100 (D) Vanadyl acetylacetonate 1 1 1 1 (Others) SBR 10 NBR 15 15 15 Evaluation Adherend PP PP PP PP Tensile shear adhesive 0.78 0.22 0.29 0.13 strength/MPa Fracture mechanism Interface Interface Interface Interface

TABLE-US-00011 TABLE 11 Reagent Example 61 First agent (A) EHMA 100 (B) Adhesive polymer 3 15 (C) Cumene hydroperoxide 5 Second agent (A) EHMA 100 (B) Adhesive polymer 3 15 (D) Vanadyl acetylacetonate 1 Evaluation Adherend PTFE Tensile shear 1.13 adhesive strength/MPa Fracture mechanism Material fracture

[0176] As is evident from the test results, the adhesive composition of the present invention is excellent in adhesion properties for various plastic resins such as low-surface energy resin base materials, for example, polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyacetal (POM), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polydimethylsilicone (PDMS), polyether ether ketone (PEEK), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), cycloolefin polymer (COP), cycloolefin copolymer (COC), polymethylpentene (PMP), and liquid crystal polyester (LCP), or high-surface energy resin base materials, for example, polyvinyl chloride (PVC), polycarbonate (PC), and polymethyl methacrylate (PMMA).

[0177] The adhesive composition of the present invention is capable of adhering to a wide range of base materials and may assume various composition forms.