ACRYLIC RUBBER AND CROSSLINKABLE COMPOSITION THEREOF

The present invention relates to an acrylic rubber and a crosslinkable composition thereof. More particularly, the present invention relates to an acrylic rubber that can suppress the reduction of oil resistance while improving cold resistance and a crosslinkable composition thereof.

Current super cold-resistant grade acrylic rubber has a cold resistance (TRIO value) of about −40° C. When acrylic rubber is used as an oil seal molding material, the use thereof in extremely cold areas is difficult in view of cold resistance. In recent years, there has been an increasing demand for use of automobiles in extremely cold areas, and acrylic rubber as an oil seal molding material that can also be used in extremely cold areas has been required.

It is thought that the cold resistance of acrylic rubber can be improved by introducing an acrylic acid alkyl ester monomer that has a longer chain length on the alkyl group side than conventional ones. However, when the alkyl chain is merely extended, oil swelling resistance, which is an important characteristic as an oil seal molding material, overly increases, and such a material cannot be used as a practical molding material.

• Patent Document 1 discloses an acrylic rubber composition compounded with silica that can improve its extrudability and roll processability without reducing its heat resistance. Patent Document 1 indicates that an alkyl (meth)acrylate-alkoxyalkyl (meth)acrylate copolymer or the like is used as the acrylic rubber; that the longer the alkyl group chain length in the alkyl (meth)acrylate is, the more advantageous in terms of cold resistance, but the less advantageous in terms of oil resistance; that these characteristics are reversed when the chain length is shorter; and that the alkoxyalkyl acrylate has an ether bond in a side chain, and thus has excellent cold resistance and oil resistance. Patent Document 1 also indicates that, from the viewpoint of the balance between cold resistance and oil resistance, Ethyl acrylate and n-butyl acrylate is preferably used as the alkyl acrylate, and 2-methoxyethyl acrylate and 2-ethxyethyl acrylate is preferably used as the alkoxyalkyl acrylate.

Further, Patent Document 2 discloses a peroxide crosslinkable acrylic rubber composition that has a high vulcanizing rate and can provide a vulcanizate having excellent normal state physical properties and compression set resistance characteristics, wherein copolymer rubber of alkyl (meth)acrylate and (meth)acrylate having an ether group forming a side chain is used as the acrylic rubber.

Patent Document 2 refers to, as the (meth)acrylate having a side chain ether group, alkoxyalkyl esters and aryloxyalkyl esters of (meth)acrylic acid, such as methoxymethyl, methoxyethyl, ethoxyethyl, butoxyethyl, ethoxypropyl and phenoxyethyl esters of (meth)acrylic acid, as well as methoxy triethylene glycol esters (Example 2)

MeO(CH₂CH₂O)₃COCH═CH₂

phenoxydiethylene glycol ester

PhO(CH₂CH₂O)₂COCH═CH₂

phenoxypolyethylene glycol

PhO(CH₂CH₂O)_nCOCH═CH₂

of (meth)acrylic acid.

However, when a methoxy triethylene glycol ester (methoxyethoxyethoxyethyl acrylate) is used, the tensile strength and elongation at break are deteriorated compared with the Examples, as shown in the results of Comparative Examples 9 and 10 described later. Further, there are problems that the value of Mooney viscosity ML₁₊₄(100° C.) is high, and that moldability is not good.

Patent Document 3 discloses an acrylic elastomer composition comprising an acrylic elastomer, an aromatic diamine compound vulcanizing agent, and a guanidine compound vulcanization aid, wherein the acrylic elastomer is obtained by copolymerizing (a) 30 to 90 wt. % of an alkyl acrylate containing an alkyl group having 1 to 8 carbon atoms, (b) 9.9 to 70 wt. % of an alkoxyalkyl acrylate containing an alkoxyalkyl group having 2 to 8 carbon atoms, (c) 0.1 to 10 wt. % of a fumaric acid mono-lower alkyl ester, and (d) 0 to 30 wt. % of a vinyl monomer or olefin monomer copolymerizable therewith. Patent Document 3 also indicates that this acrylic elastomer composition has excellent metal corrosion resistance, oil resistance, compression set characteristics, etc., and is effectively used as a vulcanization molding material for seal materials or hose materials used in parts that come into contact with metal parts and oil. A vulcanized molded product obtained from this acrylic elastomer composition has a TR-10 value of −37.1° C., which cannot satisfy the desired cold resistance.

Further, Patent Document 4 indicates that when a blend of terpolymer acrylic rubber of n-butyl acrylate, 2-methoxyethyl acrylate and vinyl monochloroacetate, and quaternary copolymer acrylic rubber obtained by further copolymerizing the terpolymer rubber and CH₂═CHCOOC₂H₄O(COC₅H₁₀O)_mCOCH₃(m: 2.11 on average) is vulcanized, a vulcanizate having excellent cold resistance (i.e., TR-10 value: −44° C.) is provided; and that the TR-10 value of the vulcanizate of the terpolymer acrylic rubber alone is merely −40° C. Moreover, when the compression set value of the blend having a TR-10 value of −44° C. is measured, a value of 59% is obtained.

• Patent Document 1: JP-A-2009-40922
• Patent Document 2: JP-A-2007-186631
• Patent Document 3: JP-A-11-92614
• Patent Document 4: JP-A-6-145257

Outline of the Invention

An object of the present invention is to provide an acrylic rubber that can suppress the reduction of oil resistance while improving cold resistance represented by a TR-10 value, and to also provide a crosslinkable composition thereof.

The above object of the present invention can be achieved by obtaining an acrylic rubber that is a copolymer in which 1 to 3 wt. % of fumaric acid monoalkyl ester monomer containing an alkyl group having 1 to 8 carbon atoms is copolymerized as a crosslinkable comonomer, wherein 45 to 65 wt. % of n-butyl acrylate, 12 to 32 wt. % of 2-methoxyethyl acrylate, and 11 to 30 wt. % of ethoxyethoxyethyl acrylate are copolymerized in 100 wt. % of comonomers other than the crosslinkable comonomer.

This ethoxyethoxyethyl acrylate copolymerized acrylic rubber is compounded with an aromatic diamine vulcanizing agent to form a crosslinkable composition.

In acrylic rubber obtained by copolymerizing the copolymer known by Patent Document 3, which is obtained by copolymerizing an alkyl acrylate containing an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl acrylate containing an alkoxyalkyl group having 2 to 8 carbon atoms, and a fumaric acid mono-lower alkyl ester, with ethoxyethoxyethyl acrylate, which is not exemplified in Patent Document 3, the introduction of ethoxyethoxyethyl acrylate with a long side chain length inhibits the aggregation of acrylic copolymer molecular chains in a low temperature range, and Tg is reduced to improve its cold resistance.

Moreover, ethoxyethoxyethyl acrylate has a higher polarity than that of alkyl acrylates with a longer side chain, such as octyl acrylate, and thus can suppress the reduction of its oil resistance while improving its cold resistance.

This alrylic rubber can be crosslinked by using an aromatic diamine vulcanizing agent that undergoes a crosslinking reaction with carboxyl groups, that are crosslinkable groups introduced into the rubber. A vulcanizate obtained from such a crosslinkable composition reduces the TR-10 value to −41.0° C. or lower to improve its cold resistance.

The acrylic rubber according to the present invention is a copolymer in which ethoxyethoxyethyl acrylate is further copolymerized in an acrylic copolymer comprising n-butyl acrylate, 2-methoxyethyl acrylate, and a fumaric acid monoalkyl ester containing an alkyl group having 1 to 8 carbon atoms.

Ethoxyethoxyethyl acrylate C₂H₅O(CH₂CH₂O)CH₂CH₂OCOCH═CH₂is used at a ratio of about 11 to 30 wt. %, preferably about 19 to 26 wt. %, in 100 wt. % of comonomers other than the crosslinkable comonomer of the resulting acrylic copolymer. If the copolymerization ratio of ethoxyethoxyethyl acrylate is less than this range, the desired effect of improving the cold resistance cannot be obtained. In contrast, if ethoxyethoxyethyl acrylate is used at a ratio larger than this range, the oil resistance, tensile strength, and compression set resistance characteristics are deteriorated.

Further, if a higher alkyl acrylate is used in place of ethoxyethyl acrylate, the oil resistance is deteriorated, as shown in Comparative Examples 7 and 8, described later.

n-Butyl acrylate, which is a main component of the acrylic copolymer, is used at a ratio of about 45 to 65 wt. %, preferably about 56 to 62 wt. %, in 100 wt. % of comonomers other than the crosslinkable comonomer of the copolymer.

Further, 2-methoxyethyl acrylate is used at a ratio of about 12 to 32 wt. %, preferably about 12 to 23 wt. %, in 100 wt. % of comonomers other than the crosslinkable comonomer of the copolymer. If 2-methoxyethyl acrylate is used at a ratio larger than this range, the desired effect of improving the cold resistance cannot be expected. In contrast, if 2-methoxyethyl acrylate is used at a ratio less than this range, its elongation at break is deteriorated.

In the acrylic copolymer, other vinyl monomers or olefin monomers, such as styrene, vinyl toluene, α-methylstyrene, vinyl naphthalene, acrylonitrile, methacrylonitrile, acrylamide, vinyl acetate, cyclohexyl acrylate and benzyl acrylate, can also be copolymerized within a range that does not inhibit the characteristics thereof (generally about 2 wt. % or less).

The fumaric acid monoalkyl ester monomer containing an alkyl group having 1 to 8 carbon atoms which is to be copolymerized in the acrylic copolymer containing these as its main components is used at a ratio of about 1 to 3 wt. %, preferably about 1 to 2.5 wt. %, in the copolymer. If the fumaric acid monoalkyl ester monomer containing an alkyl group having 1 to 8 carbon atoms is used at a ratio less than this range, the tensile strength and compression set resistance characteristics are deteriorated. In contrast, if the fumaric acid monoalkyl ester monomer is used at a ratio larger than this range, its elongation at break is reduced.

Examples of the fumaric acid monoalkyl ester monomer containing an alkyl group having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monoisopropyl fumarate, mono-n-butyl fumarate, n-hexyl fumarate, 2-ethylhexyl fumarate, and the like; preferably mono-n-butyl fumarate is used.

The acrylic copolymer comprising each of the above copolymer components is produced by a general method for copolymerizing acrylic rubber. The copolymerization reaction can be carried out by any method, such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method. An emulsion polymerization method or a suspension polymerization method is preferably adopted, and the reaction is carried out at a temperature of about −10 to 100° C., preferably about 5 to 80° C.

Examples of the polymerization initiator for the reaction include organic peroxides or hydroperoxides, such as benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide and p-methylene hydroperoxide; diazo compounds, such as azobisisobutyronitrile and azobisisobutylamidine; ammonium salts represented by ammonium persulfate; peroxide salts, such as sodium salts and potassium salts; and the like. These are used singly or as a redox system.

As an emulsifier used in the particularly preferable emulsion polymerization method, an anionic or nonionic surfactant is used as an aqueous solution or the like whose pH is optionally adjusted by acid or base, and which is formed into a buffer solution using an inorganic salt.

The polymerization reaction is continued until the conversion rate of the monomer mixture reaches 90% or more. The obtained aqueous latex is coagulated by a salt-acid coagulation method, a method using a salt, such as calcium chloride, magnesium sulfate, sodium sulfate, or ammonium sulfate, a method using a boron compound, such as boric acid or borax, a coagulation method by heat, a freeze coagulation method, or the like. The obtained copolymer is sufficiently washed with water and dried. This acrylic rubber has Mooney viscosity ML₁₊₄(100° C.) of about 5 to 100, preferably about 20 to 80.

The obtained acrylic rubber is crosslinked and molded after being compounded with an aromatic diamine compound vulcanizing agent, and preferably further a guanidine compound vulcanization aid.

Examples of usable aromatic diamine compounds include 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, p-phenylenediamine, p,p′-ethylenedianiline, 4,4′-(p-phenylenediisopropylidene)dianiline, 4,4′-(m-phenylenediisopropylidene)dianiline, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl] sulfone, bis [4-(3-aminophenoxy)phenyl] sulfone, 4,4 ′-bis (4-aminophenoxy)biphenol, bis [4-(4-aminophenoxy)phenyl] ether, 2,2-b is [4-(4-aminophenoxy)phenyl] hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and the like; preferably p-diamino substituted products are used.

Such an aromatic diamine compound is used at a ratio of about 0.1 to 5 parts by weight, preferably about 0.2 to 4 parts by weight, more preferably about 0.5 to 3 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the compounding ratio is less than this range, crosslinking is insufficient, and sufficient compression set resistance characteristics cannot be obtained. In contrast, if the aromatic diamine compound is used at a ratio larger than this range, scorch occurs, and crosslinking does not occur. On the other hand, if an aliphatic diamine compound or an alicyclic diamine compound is used, scorch is very highly likely to occur, and it is difficult to secure processing stability.

Further, examples of guanidine compounds include, in addition to guanidine, diphenylguanidine, tetramethylguanidine, tetraethylguanidine, di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salts of dicatechol borate, and the like. Of these, diphenylguanidine and di-o-tolylguanidine are preferably used.

Such guanidine compounds are used at a ratio of about 0.1 to 10 parts by weight, preferably about 0.3 to 6 parts by weight, more preferably about 0.5 to 4 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the compounding ratio is less than this range, the crosslinking rate decreases, and secondary crosslinking takes a long time, which is not practical. In contrast, if the guanidine compounds are used at a ratio larger than this range, crosslinking is inhibited, and sufficient compression set resistance characteristics cannot be obtained. When a vulcanization aid other than guanidine compounds is used, sufficient compression set resistance characteristics cannot be obtained.

After a reinforcing agent, a filler, a stabilizer, a processing aid, etc. are added to the acrylic copolymer by using a closed type kneading machine, a vulcanizing agent and a vulcanization accelerator are added by using an open roll to form a crosslinkable composition. Then, press crosslinking is performed at about 150 to 200° C. for about 1 to 30 minutes, optionally followed by oven crosslinking (secondary crosslinking) at about 150 to 180° C. for about 1 to 16 hours. Molding into a hose-like shape and crosslinking thereof are performed by injection molding or extrusion molding.

The following describes the present invention with reference to Examples.

• • (1) In a separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a Dimroth condenser tube, the following components were charged:

After nitrogen gas substitution was carried out to sufficiently remove oxygen from the system, a redox initiator comprising:

Table 1 below shows the amount of the charged monomer mixture used (parts by weight) and the amount of the produced acrylic rubber (parts by weight).

Table 2 shows the copolymerization ratio, Mooney viscosity ML₁₊₄(100° C.), and Tg value of the obtained acrylic rubber. The total amount of each monomer component, i.e., n-butyl acrylate, 2-methoxyethyl acrylate, and ethoxyethoxyethyl acrylate, is shown as 100 wt. % or 100 mol %.

(2) Using the acrylic rubber obtained in Comparative Example 1 and each Example, the following components were kneaded by using a closed type kneading machine.

The acrylic rubber crosslinked molded article was measured for each of the following items.

Normal state physical properties: According to JIS K-6253 (2010) corresponding to ISO 7619-1: 2010, and JIS K-6251 (2010) corresponding to ISO 37: 2005

Oil swelling resistance test: According to JIS K-6258 (2010) corresponding to ISO 1817: 1999

IRM 903 oil was used, and volume changes ΔV100 after being immersed at 150° C. for 70 hours were measured

TR test: According to JIS K-6261 (2006) corresponding to ISO 2921: 1997

TR-10 values were measured

Compression set: According to JIS K-6262 (2013) corresponding to ISO 815-1: 2008 and ISO 815-2: 2008, measurement values at 150° C. for 70 hours

Table 3 below shows the above measurement results. The permissible standard targets for acceptance of each physical property value are as follows: tensile strength: 10.0 MPa or more, elongation at break: 130% or more, oil swelling resistance (ΔV100): 38% or less, TR-10: −41° C. or lower, and compression set: 15% or less.

(1) In the Examples, the amounts of the charged monomer mixtures used (parts by weight) were each changed as follows.

Table 5 below shows the copolymerization ratio, Mooney viscosity ML_1-4(100° C.), and Tg value of the obtained acrylic rubber. In Comparative Example 7, the¹H-NMR peak of HA overlaps with that of n-BA, and in Comparative Examples 9 and 10, the¹H-NMR peak of MTGA overlaps with that of 2-MEA; thus, their determination is not possible. Therefore, their copolymerization ratios are unknown.

(2) Using the acrylic rubbers obtained in Comparative Examples 2 to 10, crosslinking and measurement of each item were carried out in the same manner as in Comparative Example 1 and Examples 1 to 6. Table 6 below shows the measurement results.

The above results demonstrate the following.

(1) The cold resistance (TR-10) of conventional acrylic rubber can be improved by copolymerizing 11 to 30 wt. %, preferably 19 to 26 wt. %, of ethoxyethoxyethyl acrylate (each Example).

(2) If the amount of crosslinkable monomer is too low, the compression set is deteriorated due to a decrease in crosslink density (Comparative Example 2).

(3) If the amount of crosslinkable monomer is too large, the rubber composition gets hardened, and the elongation and compression set are deteriorated (Comparative Example 3).

(4) If the amount of EEEA is too low, the effect of improving cold resistance is not sufficiently exhibited (Comparative Examples 1 and 4).

(5) If the amount of EEEA is too high, the cold resistance is improved; however, the normal state value (and compression set) are deteriorated, and the oil swelling resistance increases (Comparative Examples 5 and 6).

(6) The use of an alkyl acrylate with a longer chain than n-BA in place of ethoxyethoxyethyl acrylate improves cold resistance, but significantly increases oil swelling resistance, which is impractical (Comparative Examples 7 and 8).

(7) The use of methoxytriethylene glycol acrylate, which is a long-chain alkoxy acrylate, improves cold resistance, but deteriorates normal state physical properties (tensile strength and elongation at break) (Comparative Examples 9 and 10).