JP2003252872A - Thiol and maleimide adduct - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a maleimide adduct in which high-reactive thiol groups in a maleimide derivative are protected thereby solving problems on conventional rubber compositions, in other words, a low-temperature reaction in a formulation, scorching of the rubber in roll kneading and reduction of workability caused by reversion, to provide a rubber composition and a resin composition including the maleimide adduct. <P>SOLUTION: The maleimide adduct is represented by formula (1) (wherein R<SP>1</SP>is a 1-24C acyclo aliphatic group which may be substituted, a 5-18C alicyclic group which may be substituted, a 6-18C aromatic group which may be substituted or a 7-24C aromatic alkyl group which may be substituted, at least one of hetero element selected from the group of SO<SB>2</SB>, O, N and S may include; R<SP>2</SP>s are independently from each other a 1-24C organic group which has no active hydrogen group and may be substituted). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a maleimide adduct which is a reaction product of a thiol compound and a maleimide compound and can be used as a protective group for a thiol compound and a maleimide compound. The present invention also relates to a rubber composition containing the maleimide adduct that can be used as a vulcanization accelerator. Furthermore, the present invention relates to a resin composition containing the maleimide adduct.

[0002]

As a compound used in a rubber composition,
Compounds containing one or more thiol groups in the molecule are known. However, since the thiol group is a highly reactive substituent, it can easily react with epoxy groups, isocyanate groups and double bonds in rubber molecules in the presence of catalysts such as metal oxides and amine compounds. There is a problem that it causes a decrease in workability, such as a reaction and a high molecular weight due to an autooxidation reaction.

On the other hand, the addition of the bismaleimide compound to the rubber composition not only increases the heat resistance of the rubber but also increases the dynamic storage elastic modulus (E '), so that when the rubber composition is used in a tread. Increased steering stability is disclosed in JP-A-2000-248115 and JP-A-2001-2001.
It is described in Japanese Patent No. 64443. However, when a large amount of bismaleimide is blended with the rubber, there are problems that the vulcanization reaction is inhibited by the bismaleimide, and the bismaleimide is decomposed and gasified by the reaction with the vulcanization accelerator. In addition, the vulcanization accelerator compounded in the rubber composition causes burns of the rubber during roll kneading to reduce workability, and curing of the rubber (vulcanization) proceeds too much during vulcanization to cause reversion of vulcanization. There was also a problem.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above problems in conventional rubber compositions and contains a maleimide adduct in which a highly reactive thiol group of a maleimide compound is protected, and the maleimide adduct. A rubber composition and a resin composition are provided.

[0005]

The present inventors have found that a maleimide adduct obtained by the reaction of a specific thiol compound and a specific maleimide compound can solve the above problems, and completed the present invention. That is, the present invention provides a maleimide adduct described in (1) to (6) below,
Provided are a rubber composition and a resin composition containing the maleimide adduct.

(1) A maleimide adduct represented by the following formula (1).

[0007]

[Chemical 3]

(In the formula, R ¹ may have a substituent 1 to
Acyclic aliphatic group having 24 carbon atoms, cycloaliphatic group having 5 to 18 carbon atoms which may have a substituent, 6 to 18 carbon atoms which may have a substituent And an alkylaromatic group having 7 to 24 carbon atoms which may have a substituent, SO ₂ , O,
It may include at least one hetero element selected from the group consisting of N and S. Each R ² is independently an organic group having 1 to 24 carbon atoms which does not have an active hydrogen group and may have a substituent. )

(2) A maleimide adduct represented by the following formula (2).

[0010]

[Chemical 4]

(In the formula, n is an integer of 1 to 4, R ³ is a hydrogen atom or an acyclic aliphatic group having 1 to 24 carbon atoms which may have a substituent, and a substituent. Good 5-18
Cycloaliphatic group having 6 carbon atoms, aromatic group having 6 to 18 carbon atoms which may have a substituent, or alkyl having 7 to 24 carbon atoms which may have a substituent It represents an aromatic group and may contain at least one hetero element selected from the group consisting of SO ₂ , O, N and S. A plurality of R ³ may be the same or different. R ⁴ is an organic group having 1 to 24 carbon atoms which may have a substituent. )

(3) A rubber composition containing the maleimide adduct as described in (1) or (2) above.

(4) A resin composition containing the maleimide adduct as described in (1) or (2) above.

(5) Maleimide addition according to the above (1), which is obtained by reacting a compound (A) containing one thiol group in one molecule with a bismaleimide compound (B). Body manufacturing method.

(6) It is obtained by reacting a compound (C) containing at least one thiol group in one molecule with one or more maleimide compound (D), and the above (2) is obtained. A method for producing a maleimide adduct.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The first maleimide adduct of the present invention has the following formula (1)
It is a maleimide adduct represented by.

[0017]

[Chemical 5]

In the formula, R ¹ may have a substituent 1 to 2
An acyclic aliphatic group having 4 carbon atoms, a cycloaliphatic group having 5 to 18 carbon atoms which may have a substituent,
An aromatic group having 6 to 18 carbon atoms which may have a substituent or an alkyl aromatic group having 7 to 24 carbon atoms which may have a substituent, SO ₂ , O, It may include at least one hetero element selected from the group consisting of N and S. In addition, the substituent in the case of having a substituent is not particularly limited in the present invention. R ¹ is, for example, ethylene group, 1,6-hexyl group, 1,2
-Phenyl group, 1,3-phenylene group, 1,4-phenylene group, toluyl group, diphenyl group, ditoluyl group,
4,4'-diphenylmethane group, sulfonylbis (1,
Examples thereof include a divalent group such as a 3-phenylene) group, which is a bismaleimide compound (B) described later, excluding the maleimide group.
Among these, 1,6-hexyl group, 4,4'-diphenylmethane group, sulfonylbis (1,3-phenylene)
It is preferably a group. R ² is independently an organic group having 1 to 24 carbon atoms which does not have an active hydrogen group and may have a substituent, and is selected from the group consisting of SO ₂ , O, N and S. It preferably contains at least one hetero element selected. Here, the organic group is
Substituted by at least one atomic group selected from the group consisting of cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, alkanoyloxy group, aralkyloxy group and halogen atom It may or may not be an alkyl group, a cycloalkyl group or an aryl group, and is preferably an oxyalkyl group, an aliphatic hydrocarbon group, an aromatic group or a heterocyclic group, which is formed by combining these. It may be a substituent. It is preferably an aromatic group or a heterocyclic group because it is easily thermally dissociated as described below. Further, the substituent in the case of having a substituent is not particularly limited in the present invention, but an alkyl group or a halogen atom is preferable. Examples of R ² include methyl group, ethyl group, 1-propyl group, 2methyl-1-propyl group, 1-
Examples thereof include monovalent groups such as a butyl group, a phenyl group, a 2-thiazole group, a 2-thiazoline group, and a 2-benzothiazole group, which are excluded from the thiol group of the thiol group-containing compound (A) described later. Of these, a phenyl group, a 2-thiazoline group, and a 2-benzothiazole group are preferable.

The first maleimide adduct of the present invention is a maleimide adduct obtained by reacting a compound (A) containing one thiol group in one molecule with a bismaleimide compound (B). Is preferred. Here, the compound (A) containing one thiol group in one molecule (hereinafter,
The thiol group-containing compound (A) does not have a group having active hydrogen other than a thiol group and may have a substituent, an organic group having 1 to 24 carbon atoms and one thiol group. It is preferable that the compound is composed of and contains at least one hetero element selected from the group consisting of SO ₂ , O, N and S. Further, in the case of having a substituent, the substituent is not particularly limited as long as it does not affect the reaction with the bismaleimide compound (B), but an alkyl group or a halogen atom is preferable. Here, the organic group has the same meaning as the organic group for R ² .

From these, the thiol group-containing compound (A)
As specifically, for example, methanethiol, ethanethiol, 1-propanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol,
1-butanethiol, 2-butanethiol, 2-methyl-2-butanethiol, 2-methyl-1-butanethiol, 1-hexanethiol, 1-heptanethiol, 1
-Decanethiol, 1-dodecanethiol, n-hexadecanethiol, tert-hexadecanethiol, n
-Octadecanethiol, cyclopentanethiol, cyclohexanethiol, benzenethiol (thiophenol), 4-bromobenzenethiol, 3-chlorobenzenethiol, 4-chlorobenzenethiol, 2-fluorobenzenethiol, 3-fluorobenzenethiol, 4-fluorobenzene Thiol, 3-methoxybenzenethiol, 4-methoxybenzenethiol, 4-nitrothiophenol, 3,4-dichlorobenzenethiol, 2,3-dichlorobenzenethiol, 2,6-dichlorobenzenethiol, 3,5-dichlorobenzene Thiol, 2,4-dichlorobenzenethiol, 2,4-dimethylbenzenethiol, 2,5-dimethylbenzenethiol, 2-naphthalenethiol, 2-mercaptobenzothiazole, 5- Chill-2-mercaptobenzothiazole, 5-methoxy-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 5
-Bromo-2-mercaptobenzothiazole, 6-methyl-2-mercaptobenzothiazole, 6-methoxy-
2-mercaptobenzothiazole, 6-ethoxy-2-
Mercaptobenzothiazole, 6-chloro-2-mercaptobenzothiazole, 2-mercaptothiazole, 2
-Mercaptothiazoline, 5-methyl-1,3,4-thiadiazole-2-thiol, 2-mercaptobenzoxazole, 1-phenyl-1H-tetrazole-5-
Thiol etc. are mentioned.

Of these, a compound having an aromatic thiol group (hereinafter, also referred to as aromatic thiol) or a heterocyclic compound having a thiol group (hereinafter, also referred to as heterocyclic thiol) may be used. It is preferable because it is effective when utilizing the thermal dissociation property described later.

Further, as the thiol group-containing compound (A), 2-mercaptobenzothiazole, 5-methyl-2
-Mercaptobenzothiazole, 5-methoxy-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 5-bromo-2-mercaptobenzothiazole, 6-methyl-2-mercaptobenzothiazole, 6-methoxy-2 -Mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole,
The use of 6-chloro-2-mercaptobenzothiazole is preferable also because it works as a vulcanization accelerator after thermal dissociation described later, and it is more preferable to use 2-mercaptobenzothiazole.

Next, the bismaleimide compound (B)
Is not particularly limited as long as it is a bismaleimide compound that reacts with the thiol group-containing compound (A) to obtain the maleimide adduct represented by the formula (1). Specific examples of the bismaleimide compound (B) include 1,2-
Bismaleimide ethane, 1,6-bismaleimide hexane, N, N′-1,2-phenylenedimaleimide, N,
N'-1,3-phenylenedimaleimide, N, N'-
1,4-phenylene dimaleimide, N, N'-1,4-
Phenylene-2-methyldimaleimide, N, N'-
(1,1′-biphenyl-4,4′-diyl) bismaleimide, N, N ′-(3,3′-dimethyl-1,1′biphenyl-4,4′-diyl) bismaleimide, 4,
4'-diphenylmethane bismaleimide, N, N'-
(Methylenebis (2-chloro-4,1-phenylene))
Bismaleimide, bis (3-ethyl-5-methyl-4-
Maleimidophenyl) methane (Brand name: BMI-70)
(Kai Kasei Co., Ltd.), 2,2-bis (4-
(4-maleimidophenoxy) phenyl) propane,
N, N '-(sulfonylbis (1,3-phenylene))
Examples include dimaleimide and N, N ′-(4,4′-trimethylene glycol dibenzoate) bismaleimide. Further, a maleimide-modified polymer compound (resin, rubber, etc.) may be used. Among the exemplified compounds, 1,6-bismaleimide hexane, 1,2-bismaleimide ethane,
N, N'-1,3-phenylenedimaleimide, 4,4 '
The use of -diphenylmethane bismaleimide is preferred for economic reasons.

The reaction between the thiol group-containing compound (A) and the bismaleimide compound (B) is carried out by adding twice the equivalent amount of the thiol group-containing compound (A) to the bismaleimide compound (B) in an organic solvent. It is preferable to carry out stirring at room temperature to 150 ° C. for 1 to 24 hours. Here, the organic solvent may be any as long as both the thiol group-containing compound (A) and the bismaleimide compound (B) are soluble, and acetone, methyl ethyl ketone, N-methyl-2-
Pyrrolidone, tetrahydrofuran and N, N-dimethylformamide are preferred examples. Of these, methyl ethyl ketone and N, N-dimethylformamide are preferable because they show high solubility. After completion of the reaction, the maleimide adduct represented by the above formula (1) is obtained by concentrating and removing the organic solvent under reduced pressure.

From the above, specific examples of the maleimide adduct represented by the above formula (1) include combinations of specific examples of the above-mentioned thiol group-containing compound (A) and bismaleimide compound (B). Among them, 2-
A compound represented by the following formula (3), which is a reaction product of mercaptobenzothiazole and 1,6-bismaleimide hexane, 2-mercaptobenzothiazole and N, N′-1,
A compound represented by the following formula (4), which is a reaction product with 3-phenylene dimaleimide, and a following formula (5), which is a reaction product with 2-mercaptobenzothiazole and 4,4′-diphenylmethane bismaleimide. Compounds and the like are preferred because they are likely to undergo thermal dissociation, which will be described later.
Of these, the compounds represented by the following formulas (3) and (5) are preferable for economical reasons.

[0026]

[Chemical 6]

The second maleimide adduct of the present invention is a maleimide adduct represented by the following formula (2).

[0028]

[Chemical 7]

In the formula, n is an integer of 1 to 4, R ³ is a hydrogen atom or an acyclic aliphatic group having 1 to 24 carbon atoms which may have a substituent, and a substituent. Good cycloaliphatic group having 5 to 18 carbon atoms, aromatic group having 6 to 18 carbon atoms which may have a substituent or 7 to 24 carbon which may have a substituent It represents an alkylaromatic group having an atom and may contain at least one hetero element selected from the group consisting of SO ₂ , O, N and S. In addition, the substituent in the case of having a substituent is not particularly limited in the present invention. Further, when n is an integer of 2 to 4, a plurality of R ³ may be the same or different. Examples of R ³ include a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a cyclohexyl group, a phenyl group, and other maleimide compounds (D) described later.
And a monovalent group excluding the maleimide group. Of these, a cyclohexyl group and a phenyl group are preferable. R ⁴ is an organic group having 1 to 24 carbon atoms which may have a substituent. It preferably contains at least one hetero element selected from the group consisting of SO ₂ , O, N and S. Here, the organic group is selected from the group consisting of a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, an alkanoyloxy group, an aralkyloxy group and a halogen atom, like the organic group for R ² . An alkyl group, a cycloalkyl group or an aryl group, which may or may not be substituted with at least one atomic group, such as an oxyalkyl group, an aliphatic hydrocarbon group or an aromatic group. It is preferably a heterocyclic group, and may be a substituent formed by combining these. It is preferably an aromatic group or a heterocyclic group because it is easily thermally dissociated as described below. Further, the substituent in the case of having a substituent is not particularly limited in the present invention, but an alkyl group or a halogen atom is preferable. Examples of R ⁴ include a methyl group, a methylene group, a 2-aminoethyl group, and 2
-Aminoethylene group, 2-aminophenyl group, 1-propyl group, 1,4-butylene group, 1,6-hexyl group,
Thiols of thiol group-containing compound (C) described later such as 1,10-decyl group, phenyl group, 1,3-phenylene group, 1,5-naphthyl group, triazine group, 2-imidazole group, 2-benzothiazole group A monovalent or higher valent group excluding a group can be mentioned. Of these, a 2-benzothiazole group, a triazine group and a 2-imidazole group are preferable.

The second maleimide adduct of the present invention is a compound (C) containing at least one thiol group in one molecule.
And a maleimide adduct obtained by reacting one or more maleimide compounds (D) with each other. Compound (C) containing one or more thiol groups in the above molecule (hereinafter referred to as thiol group-containing compound (C))
Is a compound composed of an organic group having 1 to 24 carbon atoms which may have a substituent and one or more thiol groups, and is selected from the group consisting of SO ₂ , O, N and S. It preferably contains at least one hetero element selected. In addition, the substituent in the case of having a substituent is not particularly limited as long as it does not affect the reaction with the maleimide compound (D), but an alkyl group or a halogen atom is preferable. Here, the organic group has the same meaning as the organic group for R ⁴ .

From these, the thiol group-containing compound (C)
Specific examples include the compounds exemplified as the specific examples of the thiol group-containing compound (A), and further, 2-aminoethanethiol, 2-pyridinethiol, 4 having active hydrogen in addition to the thiol group. -Pyridinethiol, 2-aminobenzenethiol, 4-aminobenzenethiol, 4-hydroxybenzenethiol, 2-
Mercaptoimidazole, 2-mercaptoimidazoline, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-
5-methoxybenzimidazole, 5-amino-1,
3,4-thiadiazole-2-thiol, 3-amino-
It may be 5-mercapto-1,2,4-triazole or 5-methyl-1H-1,2,4-triazole-3-thiol. Other examples include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2- as compounds containing two or more thiol groups in one molecule. Benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,
2-ethanedithiol, 1,6-hexanedithiol,
1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propadithiol, toluene-3,
4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-
Benzenedimethanethiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,
4'-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane, 1,3. 5-triazine-2,
4,6-Trithiol (trimercapto-triazine), 2-di-n-butylamino-4,6-dimercapto-s-triazine, trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thio Glycolate), polythiol (thiochol or thiol-modified polymer (resin, rubber, etc.)) and the like.

Of these, an aromatic thiol or a heterocyclic thiol is more preferable because it is effective in utilizing the thermal dissociation property described later, and specifically,
2,5-dimercapto-1,3,4-thiadiazole,
2-di-n-butylamino-4,6-dimercapto-s
-Triazine, trimercapto-triazine are preferred. When 2,5-dimercapto-1,3,4-thiadiazole or 2-di-n-butylamino-4,6-dimercapto-s-triazine is used, the compound is solid and has no odor, and thus it is easy to handle. It is preferable because it is easily thermally dissociated as described later.

Next, the maleimide compound (D) reacts with the thiol group-containing compound (C) to give the above formula (2).
There is no particular limitation as long as it is a maleimide compound capable of obtaining a maleimide adduct represented by Maleimide compound (D)
As N-substituted maleimide, known ones can be used, but N-methylmaleimide, N-ethylmaleimide, N
N-alkyl group-substituted maleimides such as -propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-dichlorohexylmaleimide; N-cycloalkyl-substituted maleimides such as N-cyclohexylmaleimide; N
-Phenylmaleimide and the like are preferably exemplified. Among these, it is preferable to use N-cyclohexylmaleimide or N-phenylmaleimide for economical reasons.

The reaction between the thiol group-containing compound (C) and the maleimide compound (D) is carried out by adding the maleimide compound (D) to 0.90 to the thiol group-containing compound (C).
It is preferable to add 4.10 times equivalents, preferably 0.95 to 4.05 times equivalents, and stir in an organic solvent at room temperature to 150 ° C. for 1 to 24 hours. Here, the organic solvent may be any as long as both the thiol group-containing compound (C) and the bismaleimide compound (D) are soluble, and acetone, methyl ethyl ketone, N-methyl-2-
Pyrrolidone, tetrahydrofuran and N, N-dimethylformamide are preferred examples. Of these, methyl ethyl ketone and N, N-dimethylformamide are preferable because they show high solubility. After completion of the reaction, the maleimide adduct represented by the above formula (2) is obtained by concentrating and removing the organic solvent under reduced pressure.

From the above, specific examples of the maleimide adduct represented by the above formula (2) include combinations of specific examples of the above-mentioned thiol group-containing compound (C) and bismaleimide compound (D). Among them, 2-
A compound represented by the following formula (6), which is a reaction product of mercaptobenzothiazole and N-phenylmaleimide, 2-
Reaction of 2-di-n-butylamino-4,6-dimercapto-s-triazine with N-phenylmaleimide, a compound represented by the following formula (7), which is a reaction product of mercaptobenzothiazole and N-cyclohexylmaleimide. Which is a compound represented by the following formula (8), a compound represented by the following formula (9) which is a reaction product of thiophenol and N-phenylmaleimide, 2,5-dimercapto-1,
Preferred examples include compounds represented by the following formula (10), which are reaction products of 3,4-thiadiazole and N-phenylmaleimide. Among these, the following formula (6),
The compound represented by (7) is preferable because the thiol group acts as a vulcanization accelerator after thermal dissociation described below, and the compounds represented by the following formulas (8) and (10) are two thiols after thermal dissociation described below. It is preferred because of the formation of the group.

[0036]

[Chemical 8]

The maleimide adduct represented by the above formulas (1) and (2) is 150 to 250 ° C., preferably 160.
By heating at ~ 200 ° C, it has an effect of causing thermal dissociation. The thermal dissociation time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. This occurs due to thermal dissociation at the site of the maleimide compound in the maleimide adduct.

Therefore, the maleimide adducts represented by the above formulas (1) and (2) are thermally dissociated from the maleimide adduct represented by the above formula (1) to give
From the maleimide adduct represented by the formula (2), which is separately formed into the compounds represented by the following formulas (11) and (12), the following formula (13) and n (14) )
Separately produced into a compound represented by.

[0039]

[Chemical 9]

Where R ¹ , R ² , R ³ , R ⁴ and n
Are synonymous with R ¹ , R ² , R ³ , R ⁴ and n described in the above formulas (1) and (2), respectively.

Specific examples of the compounds represented by the above formulas (11), (12), (13) and (14) include, for example, the above-mentioned thiol group-containing compound (A) and bismaleimide compound (B). ), The thiol group-containing compound (C) and the maleimide compound (D), but not limited thereto.

Further, the compounds represented by the above formulas (11) and (13) have high reactivity because they have a thiol group, and when compounded in a rubber composition, a resin composition or the like, when compounded. There is a problem that the reaction occurs at a low temperature, the rubber burns during roll kneading, and the reversion of vulcanization occurs. Further, the compounds represented by the above formulas (12) and (14) have problems such as slow vulcanization during rubber vulcanization and a homopolymerization reaction. On the other hand, in the present invention, after the maleimide adduct of the present invention is added to the composition, the above formulas (11), (12) and (13) are obtained by thermal dissociation.
By separating and forming the compounds represented by (14) and (14), it becomes possible to prevent the reaction at a low temperature during the above compounding, the burning of the rubber during roll kneading, the reversion of vulcanization, the homopolymerization reaction, and the like. . That is, the above formula (1)
It means that the compounds represented by (2) and (2) function as a protecting group for the thiol group of the compounds represented by the above formulas (11) and (13) at the thermal dissociation temperature or lower.

Therefore, the maleimide adduct of the present invention is obtained by the above formulas (11) and (1) which are separately formed after thermal dissociation.
It is preferably produced in consideration of the properties of the compound represented by 3). Specifically, for example, the following formula (2) using 2-mercaptobenzothiazole which acts as a vulcanization accelerator of a sulfur vulcanized rubber is used. When the maleimide adduct of the present invention represented by 15) and (16) is used as a vulcanization accelerator of a rubber composition, it is possible to prevent a reaction at a low temperature during compounding, and workability is improved. Therefore, it is preferable. Further, as will be made clear in Examples described later, as compared with the case where 2-mercaptobenzothiazole and 1,6-bismaleimide hexane are separately used, the tensile stress at low strain is small and good. Good results have been obtained.

[0044]

[Chemical 10]

As described above, the compounds represented by the above formulas (1) and (2) protect the thiol group of the compounds represented by the above formulas (11) and (13) at the thermal dissociation temperature or lower. It functions as a base and, conversely, the above formula (1
It functions as a protecting group for the maleimide group of the compounds represented by 2) and (14). The rubber composition of the present invention containing the above maleimide adduct is a composition containing a rubber component, the maleimide adduct of the present invention and, if necessary, an additive. The rubber component used as the raw material of the rubber composition of the present invention is not particularly limited, and is a natural rubber (NR) type, isoprene rubber (IR) type, styrene / butadiene copolymer rubber (SBR) type, natural rubber / styrene / butadiene. Copolymer rubber (NR / SBR) system, natural rubber / butadiene rubber (NR / BR) system, natural rubber / acrylonitrile butadiene rubber (NR / NBR) system, natural rubber / chloroprene rubber (NR / CR) system, halogenated butyl rubber Preferred examples thereof include polychlorinated rubber, halogenated polyethylene rubber, ethylene propylene rubber (EPDM), epichlorohydrin rubber and the like.

If desired, various additives such as a filler, a plasticizer, an antioxidant, a vulcanizing agent, a vulcanization accelerator, and a vulcanization aid can be added to the rubber component. Specifically, fillers include carbon black such as HAF carbon and SAF carbon, plasticizers such as aromatic oil and wax, vulcanizing agents such as sulfur and zinc white, and accelerating vulcanization. Examples of the agent include N-cyclohexyl-2-benzothiazole sulfenamide (CBS) and dibenzothiazyl disulfide (DM), and examples of the vulcanization aid include stearic acid.

In the rubber composition of the present invention, the content of the maleimide adduct is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 100 parts by weight of the rubber component. 1 to 10 parts by weight. When the content of the maleimide adduct is within this range, there are sufficient thermal dissociation sites in the maleimide compound, which is preferable because the reaction with the rubber component after thermal dissociation easily proceeds.

The resin composition of the present invention containing the above maleimide adduct is a resin and the maleimide adduct of the present invention,
It is a composition containing an additive when necessary. The resin used as a raw material of the resin composition of the present invention is not particularly limited, and a resin having an epoxy group, an isocyanate group, or a vinyl group capable of reacting with a thiol group generated after thermal dissociation to form a crosslink is suitably exemplified. . These resins may be used alone or in combination of two or more.

The resin composition of the present invention may contain one kind or two or more kinds of polymers other than the maleimide adduct of the present invention as long as the object of the present invention is not impaired. Plasticizer, filler, catalyst, solvent, UV absorber, dye, pigment, flame retardant, reinforcing agent, antioxidant, antioxidant, thixotropic agent, surfactant (including leveling agent), dispersant, A compounding agent such as a dehydrating agent, an anticorrosive agent, an adhesion-imparting agent, an antistatic agent or the like may be contained. As these compounding agents and the like, those usually used can be used.

In the resin composition of the present invention, the content of the maleimide adduct is 1 to 300 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the resin (main component).
˜200 parts by weight, particularly preferably 10 to 100 parts by weight. When the content of the maleimide adduct is in this range, the thermal dissociation site is sufficiently present in the maleimide compound, which is preferable because the reaction with the resin after thermal dissociation is likely to proceed.

The method for producing the rubber composition and the resin composition of the present invention is not particularly limited. For example, the above-mentioned essential components and optional components are appropriately added to a reaction vessel, and a stirrer such as a mixing mixer is placed under reduced pressure. It can be obtained by thoroughly kneading.

The rubber composition and resin composition of the present invention are
It can be used for various adhesives, adhesives, paints, sealing materials and the like.

[0053]

The present invention will be described in detail with reference to the following examples. However, the present invention is not limited to this. (Example 1) 1,6-in 50 g of methyl ethyl ketone
27.6 g (0.1 mol) of bismaleimidohexane and 33.4 g (0.2 m) of 2-mercaptobenzothiazole.
ol) was added, and the mixture was reacted at 100 ° C. for 12 hours.
After completion of the reaction, methyl ethyl ketone was removed under reduced pressure at 90 ° C. to obtain 60.5 g (reaction yield 99%) of a maleimide adduct (adduct 1) represented by the following formula (15). ¹ H-
NMR (deuterated chloroform) δ (ppm): 1.3-1.
7, 3.0, 3.2-3.6, 4.5, 7.3-7.
9.

Example 2 In 70 g of methyl ethyl ketone, 40.8 g (0.1 mol) of N, N '-(sulfonylbis (1,3-phenylene)) dimaleimide and 2-
33.4 g of mercaptobenzothiazole (0.2 mo
1) and were added and reacted at 100 ° C. for 12 hours. After the reaction was completed, methyl ethyl ketone was removed under reduced pressure at 90 ° C,
73.2 g (reaction yield 99%) of a maleimide adduct (adduct 2) represented by the following formula (16) was obtained. ¹ H-N
MR (heavy chloroform) δ (ppm): 3.2.
6, 4.5, 7.2-7.9.

[0055]

[Chemical 11]

(Examples 3, 4 and Comparative Example 1) The obtained maleimide adducts (adduct 1 and adduct 2) are shown in Table 1 below.
In the composition components (parts by weight) shown in Example 1, polyisopropylene rubber, carbon black, zinc oxide, stearic acid, an antioxidant and sulfur are mixed and uniformly dispersed in a high-viscosity mixing mixer. A rubber composition was used. In addition, polyisopropylene rubber, carbon black, zinc oxide, stearic acid, anti-aging agent, sulfur, N-cyclohexyl-2-benzo, with the composition components (parts by weight) shown in Table 1 below without adding a maleimide adduct. Thiazole sulfenamide (CZ) was mixed and uniformly dispersed with a mixing mixer for high viscosity to obtain a rubber composition of Comparative Example 1.

The following compounds were used as the above components. Nipol as polyisopropylene rubber
IR2200 (manufactured by Zeon Corporation) was used, and SAF (manufactured by Showa Black) was used as the carbon black.
LUYAC YA (manufactured by NOF CORPORATION) was used as stearic acid, Nocrac 224 (manufactured by Ouchi Shinko Chemical Co., Ltd.) as an antioxidant, and powdered sulfur (manufactured by Karuizawa Smelting Co., Ltd.) as sulfur.

[0058]

[Table 1]

The vulcanization characteristics of the rubber compositions of Comparative Example 1, Examples 3 and 4 were examined under the following conditions. The results are shown in FIGS. 1 and 2. <Vulcanization Properties> The rubber compositions of Comparative Example 1, Examples 3 and 4 were treated at 160 ° C. for 60 minutes or 180 ° C. for 6 minutes, respectively.
Vulcanized in 0 minutes, vulcanization time (min) and torque (Nm)
Was measured in accordance with the test method of SRIS-3102 (standard of Japan Rubber Association). From FIGS. 1 and 2, the rubber compositions of Examples 3 and 4 were compared with the rubber composition of Comparative Example 1, and the result was that the reversion to vulcanization accompanied by a decrease in torque was suppressed. In addition, the rubber composition of Example 3 has 180
When vulcanized at 60 ° C. for 60 minutes, as shown in FIG. 2, the torque slightly increased even in the latter half of vulcanization.

(Examples 5 and 6, Comparative Examples 2 and 3) 2-mercaptobenzothiazole (hereinafter abbreviated as M) 1,6-
Bismaleimide hexane (hereinafter abbreviated as H-MI), adduct 2 represented by the above formula (16) (hereinafter M-SO ₂ M)
(Abbreviated as I) in the composition components (parts by weight) shown in Table 2 below, polyisopropylene rubber, carbon black, zinc oxide,
Examples 5, 6 and Comparative Example 2 were prepared by mixing with stearic acid, an antioxidant and sulfur and uniformly dispersing with a high viscosity mixing mixer.
And rubber compositions 3 and 3.

The following compounds were used as the above components. Nipol as polyisopropylene rubber
IR2200 (manufactured by Zeon Corporation) was used, and SAF (manufactured by Showa Black) was used as the carbon black.
LUYAC YA (manufactured by NOF CORPORATION) was used as stearic acid, Nocrac 224 (manufactured by Ouchi Shinko Chemical Co., Ltd.) as an antioxidant, and powdered sulfur (manufactured by Karuizawa Smelting Co., Ltd.) as sulfur.

[0062]

[Table 2]

Physical properties of the rubber compositions of Comparative Examples 2 and 3 and Examples 5 and 6 after vulcanization were examined under the following conditions.
The results are shown in FIG. 3 and Table 2. <Tensile Test> A tensile test (measurement of tensile stress) and a hardness test were performed in accordance with JIS-K6301-1995. The rubber composition was vulcanized at 160 ° C. for 30 minutes. As shown in FIG. 3 and Table 2, the rubber compositions of Examples 5 and 6 resulted in smaller tensile stress and smaller hardness than the rubber composition of Comparative Example 3. Therefore, rather than mixing M and H-MI separately, M-SO prepared by reacting M and H-MI in advance was used.
It was found that the mixture of ₂ MI was superior because the result was about the same as the formulation used for the existing tire shown in Comparative Example 2. Also, regarding the heat resistance, it was found that the rubber compositions of Examples 5 and 6 were superior to the rubber composition of Comparative Example 2 because the bismaleimide compound was compounded.

[0064]

Industrial Applicability As described above, the maleimide adduct of the present invention in which a highly reactive thiol group is protected is used in a rubber composition and a resin composition to give a composition excellent in workability, particularly When used as a vulcanization accelerator in a rubber composition, it is possible to obtain a composition capable of suppressing the reaction at a low temperature during compounding, the burning of the rubber during roll kneading, and the reversion of vulcanization. This facilitates the use of the rubber composition and the resin composition utilizing the high reactivity of the thiol group, so that the rubber composition and the resin composition using the maleimide adduct of the present invention are very useful. Is.

[Brief description of drawings]

FIG. 1 is a relationship between vulcanization time and torque when the rubber compositions of Comparative Example 1, Examples 3 and 4 are vulcanized at 160 ° C. for 60 minutes.

FIG. 2 is a relationship between vulcanization time and torque when the rubber compositions of Comparative Example 1, Examples 3 and 4 were vulcanized at 180 ° C. for 60 minutes.

FIG. 3 is the result of a tensile test of the rubber compositions of Comparative Examples 2 and 3 and Examples 5 and 6 after vulcanization.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C063 BB08 CC62 DD04 EE10                 4J002 AA001 AC001 AC011 AC061                       AC071 AC081 AC091 AC121                       BB151 BB241 CH041 EV086                       FD146 FD206 GT00

Claims (4)

[Claims] 1. A maleimide adduct represented by the following formula (1). [Chemical 1] (In the formula, R ¹ is a non-cyclic aliphatic group having 1 to 24 carbon atoms which may have a substituent, and optionally 5
A cycloaliphatic group having 18 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms which may have a substituent or 7 to 24 carbon atoms which may have a substituent It represents an alkyl aromatic group having and may contain at least one hetero element selected from the group consisting of SO ₂ , O, N and S. Each R ² is independently an organic group having 1 to 24 carbon atoms which does not have an active hydrogen group and may have a substituent. ) 2. A maleimide adduct represented by the following formula (2). [Chemical 2] (In the formula, n is an integer of 1 to 4, R ³ is a hydrogen atom or an acyclic aliphatic group having 1 to 24 carbon atoms which may have a substituent, and an optionally substituted 5 To cycloaliphatic groups having 18 carbon atoms, optionally substituted 6 to 18
Shows an aromatic group having 6 carbon atoms or an alkyl aromatic group having 7 to 24 carbon atoms which may have a substituent, and is at least selected from the group consisting of SO ₂ , O, N and S. You may include 1 type of hetero element. A plurality of R ³ may be the same or different. R ⁴
Is an organic group having 1 to 24 carbon atoms which may have a substituent. ) 3. A rubber composition comprising the maleimide adduct according to claim 1 or 2. 4. A resin composition containing the maleimide adduct according to claim 1 or 2.