JPH02235977A - Epoxy resin adhesive composition - Google Patents

Abstract

PURPOSE:To prepare an adhesive compsn. excellent in the durability of adhesion such as the water resistance of adhesion by mixing a curing agent with a main component comprising a mixture of an epoxy resin with a specific modified hydrocarbon resin produced from a coal-derived oil. CONSTITUTION:An arom. olefin (e.g. coumarone), which is derived from a gas oil produced in dry distillation of coal or from a fraction at 130 to 200 deg.C obtd. by distillation of coal tar, is copolymerized in the presence of 2 to 20wt.% (based on total reactants) phenol to give a phenol-modified hydrocarbon resin, which is reacted with epichlorohydrin to produce an epoxy-modified hydrocarbon resin. Said phenol-modified or epoxy-modified hydrocarbon resin is mixed with an epoxy resin, and the resulting mixture as a main component is mixed with a curing agent (e.g. dicyandiamide) to produce an epoxy resin adhesive compsn.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides an epoxy resin adhesive composition suitable for use in the field of adhesives used for manufacturing and assembling vehicles such as railway vehicles, aircraft, ships, home appliances, electronic parts, etc. It is about things.

[Conventional Technique 441i] Evogishi resin compositions containing a hydrocarbon resin as the main ingredient are aromatic non-aromatic resins with a boiling point range of 140 to 280'c obtained during thermal decomposition of petroleum as a hydrocarbon resin. The power method uses epoxy-modified petroleum resin obtained by polymerizing a saturated hydrocarbon fraction with peracetic acid and introduces epoxy groups into T4, or the hydrocarbon resin is coumaron-indene resin. Phenol is added to the raw material oil. , 6% by weight or more of one or more selected from alkyl derivatives of phenol.
Methods of using added and polymerized phenol-modified coumaron-indene resin in paints are known, and are disclosed in JP-A-54-1.800.0 and JP-A-63-18396, respectively.
It is disclosed in Publication No. 6.

[Problems to be Solved by the Invention] However, although these conventional methods are effective in improving water resistance and chemical resistance when used as paints, and in improving paint film blistering, they cannot be used for more advanced methods. Application to the field of adhesives, which requires water-resistant adhesive properties, has not yet been attempted.

Considering the shortcomings of the conventional technology, the present inventors aimed to develop an epoxy resin adhesive composition with excellent adhesive properties by blending a modified hydrocarbon resin synthesized from petroleum-based raw material oil. conducted research.

[Means for Solving the Problems] As a result of research to solve the above-mentioned problems, the present inventors used a mixture of an epoxy resin and a specific modified hydrocarbon resin as a main ingredient, and added a curing agent to this mixture. It has been discovered that an epoxy resin adhesive composition containing the following has extremely excellent adhesive properties, and the present invention has been completed.

Epoxy resins used in the present invention are not particularly limited, but include, for example, bisphenol A epoxy resins and novolanque phenol resin epoxy resins having an average molecular weight of 300 to 4000 and an epoxy equivalent of 180 to 3500 g/eq. Resin etc. can be used. In addition,
This epoxy resin does not contain epoxy-modified hydrocarbon resin.

Modified hydrocarbon resin is a 130-20% hydrocarbon resin obtained by distillation of gas light oil or coal tar produced during coal carbonization.
A phenol-modified hydrocarbon obtained by copolymerizing the 0'C fraction as a raw material and copolymerizing the aromatic olefins contained therein, such as coumaron and indene, with phenols present in an amount of 2 to 20% of the total. This is an epoxy-modified hydrocarbon resin synthesized by addition condensation of shrimp chlorhythrin to a resin or the phenol-modified hydrocarbon resin.

Here, the phenol-modified hydrocarbon resin has a structure in which one molecule of phenol is added to the end of one polymer chain of an aromatic olefin such as coumaron or indene, and the manufacturing conditions for the usual coumaron-indene resin can be used as is. It is possible to apply and manufacture. That is, the acid catalysts used include brenstenotic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid, boron trifluoride and its complexes, Lewis acids such as aluminum chloride, solid acids such as acid clay, activated clay, and acidic ion exchange resins. The polymerization conditions also vary depending on the type of acid catalyst used, the type and concentration of monomers, and the target average molecular weight and softening point, but the amount of catalyst used relative to the feedstock oil is 0.5 to 2.0% for Lewis acids. ．． 0% by weight, 1 to 10% by weight for Brønsted acids, 5 to 10% by weight for solid acids
50% double star is preferred. In addition, the reaction temperature is 50 to 15
0'C and the reaction time is preferably 0.5 to 7 hours. The polymerized oil is decatalyzed by washing with water or alkali using a conventional method, and the solvent is evaporated by distillation to obtain a phenol-modified hydrocarbon resin.

On the other hand, in the synthesis of epoxy-modified hydrocarbon resin,
The method disclosed in Japanese Patent No. 1-99218, etc. can be used. That is, it can be synthesized by reacting the phenol-modified hydrocarbon resin with shrimp chlorohydrin in the presence of an alkali.

Specifically, an excess of shrimp chlorohydrin in an amount of 6 times the mole or more relative to the number of moles of phenolic hydroxyl groups in the phenol-modified hydrocarbon resin is added to an aqueous alkaline solution such as sodium hydroxide or potassium hydroxide at 50 to 100'C. After completion of the reaction, surplus alkali is removed by activated clay,
Neutralize with a solid acid such as acid clay, acidic ion exchange resin, solid phosphoric acid, etc., separate the solid acid from the system together with the salt produced during the reaction, and then remove excess shrimp chlorhythrin by distillation. Evaporate to obtain a modified hydrocarbon resin.

Through this manufacturing method, epoxy resin adhesive compositions made by blending amine-based curing agents such as polyamide-based, amine-adduct-based, and modified polyamine-based hardeners with a base agent mainly composed of modified hydrocarbon resin and epoxy resin have excellent adhesive properties. Demonstrate characteristics. The ratio of epoxy resin and modified hydrocarbon resin is 100 for the former.
10 to 200 parts by weight of the latter, preferably 2 parts by weight
It is 0 to 100 parts by weight.

[Function] Since the modified hydrocarbon resin used in the epoxy resin adhesive composition of the present invention is copolymerized with highly polar oxygen-containing components such as coumaron, phenols, and epoxidized phenols, there is no compatibility with the epoxy resin. It is presumed that the solubility and reactivity with the curing agent become better, and the effect of relieving internal stress generated during curing of the composition increases. As a result, it is thought that the adhesion between the adhesive layer and the adherend is improved, and various adhesive durability such as water resistance is improved. However, if the copolymerization rate of phenol is increased beyond the range of the present invention, the water resistance etc. will be impaired due to the hydrophilic nature of phenol.

〔Example〕

Examples of the present invention will be described below.

Tip opening 1 Bisphenol A type epoxy resin (manufactured by Asahi Kasei Corporation, A
ER337, epoxy N250 g/eq)
100 parts by weight and 50 parts by weight of modified hydrocarbon resin A whose composition and properties are shown in Table 1 were dissolved in toluene to obtain 90%
A 70% by weight solution was mixed to prepare the main cutting.

Next, as a curing agent, polyamide (manufactured by Dainippon Ink & Chemicals, Laccamide TD973, active hydrogen equivalent: 17
8 g/eq) at an equivalent ratio of 0.8, that is, 6
An adhesive was prepared by dissolving 9 parts by weight in a 7:3 mixed solvent of toluene:isopropyl alcohol to form a 70% by weight solution, and a test piece was prepared and prepared according to the following procedures and conditions. A water resistant adhesion test was conducted.

■Test piece preparation method Two aluminum plates (25xl25xO.5
After applying adhesive to each piece (mm) using a #l2 bar coater, the two sheets were pasted together and heated at 180°C for 3 hours under a load of 6k.
g to prepare a test piece.

■Water resistance test method The test piece was immersed in water for two weeks at room temperature.

■Adhesion test method Compliant with JIS K 6854 T-type peel test method. Here, the pulling speed is 50mm/lnin
The measurement atmosphere temperature was 25°C.

The test results are shown in Table 2. Both the initial adhesive strength and the adhesive strength after immersion in water were good.

Tip 2 An adhesive was prepared in the same manner as in Example 1, except that modified hydrocarbon resin B was used, and its initial adhesive strength and water-resistant adhesive properties were evaluated.

The test results are shown in Table 2. The initial adhesive strength was further improved compared to Example 1, and the water resistance was also good.

Comparison ±1 An adhesive was prepared in the same manner as in Example 1, except that the modified hydrocarbon resin was not blended, and the same evaluation was performed.

The test results are shown in Table 2, and the water resistant adhesive strength was poor.

Hokukaikan 2 to 4 Modified hydrocarbon resin C, D instead of modified hydrocarbon resin A
Alternatively, an adhesive was prepared in the same manner as in Example 1, except that a commercially available phenol-modified petroleum resin was used, and the same evaluation was performed.

The results are shown in Table 2. Comparative Examples 2 and 4 had poor water-resistant adhesive strength, and Comparative Example 3 had poor initial adhesive strength.

(1) Manufactured by Asahi Kasei Corporation ■, AER 3 3 7 (2) Manufactured by Nippon Petrochemical ■, Nisseki Neopolymer E100 (3) Manufactured by Dainippon Ink & Chemicals ■, Laccamide TD (Effect of the invention) Epoxy resin adhesion according to the present invention Since the agent composition has excellent adhesive durability including water-resistant adhesive properties, it can be used in adhesive fields where adhesive durability is required, such as for vehicles such as railway cars, ships, home appliances, etc.

Procedural master's letter (spontaneous) 1. Case Description 1999 Patent Application No. 57172 2. Name of the invention Epoxy resin adhesive composition 3. Relationship with the person making the amendment Patent applicant address 5-13-16 Ginza, Chuo-ku, Tokyo Name (6
64) Nippon Steel Chemical Co., Ltd. Representative Enji Moriguchi 4. Agent 101 Address 2-10-25 Iwamotocho, Chiyoda-ku, Tokyo. Date of amendment order Voluntary amendment 11 Contents of amendment ■, Detailed explanation of the invention column (1) The following sentence is added between lines 3 and 4 on page 9 of the specification.

”!JMJM 3 Nitrile rubber modified liquid epoxy resin (manufactured by Asahi Denka Kogyo ■,
Product Name: Adekal Resin El"4024, Epoxy Equivalent -210~250 g/eq) 50g Modified Hydrocarbon Resin B, 10 whose composition and properties are shown in Table 1
The pulverized product of g was added and dissolved by heating to prepare a main ingredient.

Next, dicyandiamide (Shikoku Kasei Kogyo) was used as a curing agent.
(active hydrogen equivalent: -21 g/eq) was added to the main ingredient so that the equivalent ratio was 0.8, that is, 4.1 g, and mixed with thorough stirring.

Next, test pieces were prepared according to the following procedures and conditions, and each adhesive strength test of moisture-resistant adhesive strength and heat-resistant adhesive strength was conducted.

■Test piece preparation method a, for T-type peel test: After applying the above adhesive in an area of 25 x 100 mm using a #12 bar coater to each of two aluminum plates (dimensions: 25 x 125 x 0.5 n + n +) as adherends. , two sheets were bonded together and heat-cured at 180° C. for 30 minutes to prepare a test piece.

b. For shear strength test: Using a #12 bar coater, 12. After applying the above adhesive in an area of 5 x 2 5 mlpl, the two sheets were bonded together and heat cured under the same conditions to prepare a test piece.

■Moisture resistance test method The above test piece was tested at 50'C. 95%R. H. The adhesive strength was measured over time after 14 days and 30 days after storage in a constant temperature and humidity chamber under the following environmental conditions, and compared with the initial adhesive strength.

(2) Heat Resistance Test Method The above test piece was stored in a safety oven under an environmental condition of 90°C, and the adhesive strength over time was measured after 14 days and 30 days, and compared with the initial adhesive strength.

■Adhesion test method a. T-type peel test method: Based on the T-type peel test method of JIS K 6854. Here, the pulling speed was 50 mm/min, and the measurement atmosphere temperature was 25°C.

b. Tensile shear strength test method: Based on JIS K6850 tensile shear adhesive strength test method. Here, the pulling speed was 200 ml/min, and the measurement atmosphere temperature was 25°C.

The test results are shown in Table 3. In addition to excellent initial adhesion,
The aging deterioration at high temperatures and under high temperatures was also small. ” (2) On the bottom line of page 9, after “was.”, add the following sentence on a new line.

Comparison 5 An adhesive was prepared in the same manner as in Example 3, except that modified hydrocarbon resin B was not added, and an adhesive strength test was conducted under the same conditions.

The test results are shown in Table 3. Initial adhesive strength was low, and deterioration over time under high temperature and high humidity was significant.

Comparison M6-8 Instead of modified hydrocarbon resin B, modified hydrocarbon resin C, commercially available petroleum resin (manufactured by Nippon Petroleum Chemical Co., Ltd., trade name: Nippon Seki Neopolymer 100), commercially available phenol-modified petroleum resin (Nippon Oil Co., Ltd.) Manufactured by Kagaku O@, trade name: Futatsuki Neobolymer E-10
An adhesive was prepared in the same manner as in Example 3, except that 0) was added, and an adhesive strength test was conducted in the same manner.

The test results are shown in Table 3. Initial adhesive strength was low, and deterioration over time under high temperature and high humidity was significant. (3) Insert Table 3 as shown in the attached sheet between lines 4 and 5 on page 11.

Attachment 3: Manufactured by Asahi Denka Kogyo ■, product name: ADEKA RESIN EP-4024
Manufactured by Nippon Petrochemical ■, Product name: Nisseki Neopolymer 100 Manufactured by Nippon Petrochemical ■, Product name: Nisseki Neopolymer E Manufactured by Shikoku Kasei Kogyo ■

Claims (1)

[Claims] The main ingredient is a mixture of epoxy resin and modified hydrocarbon resin,
This is an epoxy resin adhesive composition made by blending this with a curing agent, and the modified hydrocarbon resin here is a 130-200°C fraction obtained by distillation of gas light oil or coal tar produced during coal carbonization. As a raw material, 2 to 20% by weight of phenols are added to the aromatic olefin contained therein.
An epoxy resin adhesive composition characterized in that it is a phenol-modified hydrocarbon resin copolymerized in the presence of a phenol-modified hydrocarbon resin, or an epoxy-modified hydrocarbon resin synthesized by addition condensation of epichlorohydrin to the phenol-modified hydrocarbon resin.