JPH0693150A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. which gives a cured article excellent in mechanical characteristics, weatherability, heat resistance, etc., by compounding a specific isobutylene polymer and a specific polyepoxy compd. CONSTITUTION:The compsn. contains a phenol-group-contg. isobutylene polymer having, on average, more than 1.0 group of formula I (wherein R1 is H, CH3, or C2H5) per molecule and a polyepoxy compd. having, on average, more than 1.0 epoxy group per molecule (e.g. Epikote 828).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel curable resin and a curable resin composition containing them, and more specifically, a curable resin capable of imparting excellent mechanical properties, weather resistance, heat resistance and the like to the cured product. And a curable resin composition containing them.

[0002]

2. Description of the Related Art Conventionally, as room temperature curable resin compositions,
Various types have been developed, but a curable resin composition capable of imparting excellent mechanical properties, weather resistance, and heat resistance to a cured product has hardly been developed. An isobutylene-based polymer having an average of more than one functional group per molecule can be crosslinked to form a rubber-like cured product as it is or by further performing various functional group conversion reactions.
Further, this polymer is described in USP 4,904,732 and JP-A-63-6.
A moisture-curable polymer can be obtained by introducing a crosslinkable silicon group as disclosed in JP-A-041. However, this method requires supply of water, and there is a problem in terms of curing speed and the like. Further, an isobutylene-based polymer having an average of more than one functional group per molecule is US
P 3,644,315 and USP 4,524,187,
This polymer is obtained by copolymerizing isobutylene and a compound having a conjugated double bond, has a double bond in the main chain, and has poor weather resistance, chemical resistance and reactivity. Is.

[0003]

An object of the present invention is to provide a curable resin composition capable of imparting excellent mechanical properties, weather resistance, heat resistance and the like to a cured product.

[0004]

That is, the present invention provides (A)
An average of more than 1.0 formula (1) per molecule:

[0005]

[Chemical 3]

[In the formula, R ₁ represents a hydrogen atom, a methyl group or an ethyl group. ] A phenol group-containing isobutylene-based polymer having a unit represented by: and (B) a polyfunctionality having an average of more than 1.0 epoxy groups per molecule. The present invention relates to a curable resin composition containing an epoxy compound.

In the general formula (1), R ₁ is preferably a hydrogen atom, a methyl group or an ethyl group.

The isobutylene polymer having a phenol group in the present invention is a polymer characterized by having at least a unit represented by the general formula (1).
The number average molecular weight of the isobutylene monomer unit is 500 to 500,000, more preferably 1,0.
It is a polymer of 00 to 50,000. The average number of molecules per molecule is preferably more than 1, more preferably 1.
The number of units represented by the general formula (1) is not less than 05, more preferably not less than 1.1 and not more than 10, and most preferably not less than 1.1 and not more than 5. The unit represented by the general formula (1) is preferably present as a side chain, but may be present at the terminal. Number average molecular weight is 50
When it is less than 0, the content of the isobutylene unit is small, and the properties as an isobutylene polymer cannot be expressed, and the content is 500,00.
When it exceeds 0, the polymer becomes resinous and becomes difficult to handle. Further, it is preferable that the polymer of the present invention has substantially no unsaturated bond in the main chain from the viewpoint of weather resistance and the like.

In the present specification, the isobutylene polymer means a polymer of a cationically polymerizable monomer containing isobutylene. Here, the cationically polymerizable monomer containing isobutylene is not limited to a monomer consisting of isobutylene alone, but may be 50% of isobutylene.
It means a monomer in which a weight percent (hereinafter simply referred to as “%”) or less is replaced with a cationically polymerizable monomer capable of copolymerizing with isobutylene. Examples of the cationically polymerizable monomer that can be copolymerized with isobutylene include olefins having 3 to 12 carbon atoms, conjugated dienes, vinyl ethers, aromatic vinyl compounds, vinylsilanes and the like. Of these, olefins having 3 to 12 carbon atoms and conjugated dienes are preferable, but when weather resistance and the like are a problem, olefins other than conjugated dienes are preferable.

Specific examples of the cationically polymerizable monomer copolymerizable with the above isobutylene include propylene and
1-butene, 2-butene, 2-methyl-1-butene, 3
-Methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene. , Dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimetolsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl -1,1,
Examples include 3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.
Among these, for example, propylene, 1-butene, 2-butene, styrene, butadiene, isoprene, cyclopentadiene and the like are preferable. These cationically polymerizable monomers copolymerizable with isobutylene may be used alone or in combination with two or more kinds.

Average of 1.0 per molecule in the present invention
More than general formula (1):

[0012]

[Chemical 4]

[In the formula, R ₁ represents a hydrogen atom, a methyl group or an ethyl group. ] In order to obtain an isobutylene polymer having a phenol group, which has a unit represented by: .

As the polyfunctional epoxy compound in the present invention, known ones can be widely used as long as they are polyfunctional epoxy compounds having an average of 1.0 or more epoxy groups per molecule. It may be unknown. It may be a mixture of two or more different types.
As the polyfunctional epoxy compound used in the present invention, for example, those described in "New Epoxy Resin" (written by Hiroshi Kakiuchi, Shokoido Co., Ltd., issued May 10, 1985) can be used. The addition amount of the polyfunctional epoxy compound in the present invention is 0.001 to 10 epoxy groups based on the phenol groups in the phenol group-containing isobutylene polymer.
000 equivalents, preferably 0.01 to 1000 equivalents, more preferably 0.1 to 50 equivalents, still more preferably 0.5 to
The amount is 10 equivalents.

Various catalysts can be added to the curable resin composition of the present invention in order to effectively carry out the reaction between the phenol group-containing isobutylene polymer and the polyfunctional epoxy compound. As the catalyst to be used, those widely known as catalysts for addition reaction of phenolic hydroxyl groups and epoxy groups can be widely used. Also, a catalyst which is unknown at present may be used.

Examples of the reaction catalyst include imidazoles such as 1,2-dimethylimidazole and 2-methylimidazole, amines such as trimethylamine and triethylamine, tetramethylmethylammonium bromide,
Examples thereof include ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine, and phosphonium salts such as benzyltriphenylphosphonium chloride.

When the curing catalyst is used, the amount used is preferably 0.01 to 100 parts with respect to 100 parts of the curable resin,
0.1 to 10 parts is more preferable. If the amount of the curing catalyst used is too small, the curing speed will be slow and the curing reaction will not proceed sufficiently, which is not preferable. On the other hand, if the amount of the curing catalyst used is too large, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product, which is not preferable.

The composition of the present invention may further contain, if necessary, an adhesiveness improving agent, a physical property adjusting agent, a storage stability improving agent, a plasticizer,
Filler, anti-aging agent, ultraviolet absorber, metal deactivator,
Various additives such as an ozone deterioration inhibitor, a light stabilizer, an amine-based radical chain inhibitor, a phosphorus-based peroxide decomposing agent, a lubricant, a pigment and a foaming agent can be appropriately added.

[0019]

EXAMPLES Next, the present invention will be further clarified with reference to examples, but the present invention is not limited to the examples. Synthesis Example 1 A 100 ml pressure-resistant glass autoclave was equipped with stirring blades, a three-way cock, and a vacuum line, and the polymerization container was dried by heating at 100 ° C. for 1 hour while drawing a vacuum in the vacuum line, and then cooled to room temperature. The pressure was returned to normal pressure with nitrogen using a cock. Then, while flowing nitrogen from one of the three-way cocks, 40 ml of methylene chloride, which is the main solvent dried by calcium hydride treatment, was introduced into the autoclave using a syringe. Then 20 mmol of distilled and purified tert-butoxystyrene was added. Next, a pressure-resistant glass liquefied gas sampling tube with a needle valve containing 7 g (125 mmol) of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock, and then the container body was placed at -70 ° C. It was immersed in the dry ice-acetone bath, and the inside of the polymerization vessel was cooled for 1 hour while stirring. After cooling, the inside of the container was decompressed by a vacuum line, the needle valve was opened, and isobutylene was introduced from the pressure-resistant glass liquefied gas sampling tube into the polymerization container. After that, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, cooling was further continued for 1 hour with stirring, and the inside of the polymerization vessel was heated to -30 ° C.

Next, 3.2 g (17 mmol) of TiCl _{4 was} added.
Was added from a three-way cock using a syringe to start the polymerization, and when 60 minutes had passed, methanol precooled to 0 ° C. or lower was added to complete the polymerization. Then, concentrated hydrochloric acid was added to the reaction mixture, and the mixture was reacted at 60 ° C. for 5 hours. Thereafter, unreacted isobutylene, methylene chloride, tert-butoxystyrene, methanol and the like were distilled off, the remaining polymer was dissolved in 100 ml of n-hexane, and this solution was repeatedly washed with water until it became neutral. Then, the n-hexane solution was concentrated to 20 ml,
The polymer was precipitated by pouring this concentrated solution into 0 ml of acetone. The polymer thus obtained was again dissolved in 100 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain 3.6 g of an isobutylene polymer. The structure of the obtained polymer is analyzed by 1H-NMR.
(300 MHz) method. As a result, a phenol group-containing isobutylene polymer having 3.8 phenyl groups in one molecule was obtained.

Example 1 2 parts of Epicoat 828 (bifunctional epoxy compound) and 0.1 part of triethylamine were added to 100 parts of the phenol group-containing isobutylene polymer obtained in Synthesis Example 1,
Hardened bumps were created. The obtained cured product showed good tensile properties. Further, when these cured products were placed in an oven at 100 ° C. and subjected to a heat resistance test, no change such as surface dissolution was observed in any of the samples after 300 hours. In the weather resistance test using a sunshine weather meter, no significant change was observed on the surface after 1,000 hours.

[0022]

The cured product of the curable resin of the present invention has excellent mechanical properties, weather resistance and heat resistance.

Claims (3)

[Claims] 1. (A) A general formula (1) having an average of more than 1.0 per molecule: [In the formula, R ₁ represents a hydrogen atom, a methyl group or an ethyl group. ] A phenol group-containing isobutylene-based polymer having a unit represented by: and (B) a polyfunctionality having an average of more than 1.0 epoxy groups per molecule. A curable resin composition containing an epoxy compound. 2. A phenol group-containing isobutylene-based polymer is a polymer mainly composed of isobutylene monomer units and having a number average molecular weight of 500 to 500,000, and more than one compound represented by the general formula (1) on average per molecule. ): [Chemical 2] [In the formula, R ₁ is the same as above. ] The curable resin composition according to claim 1, which is an isobutylene-based polymer having a unit represented by the following formula in the polymer. 3. The curable resin composition according to claim 1, which has substantially no unsaturated bond in the main chain of the curable resin.