JP2010047685A - Method for producing (meth)acrylate polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide economical and efficient purification conditions for suppressing hydrolysis of an acetate while securing a degree of purification of the polymer, in high-temperature adsorption treatment of a (meth)acrylate polymer using the acetate which is a nonaromatic compound as a solvent. <P>SOLUTION: A (meth)acrylate polymer is subjected to adsorption purification at ≥150°C using an acetate as a solvent in place of an aromatic compound. Aluminum silicate and hydrotalcite are used together as an adsorbent and the amount of the aluminum silicate is controlled to 0.05-0.5 pt.wt. based on 100 pts.wt. of the polymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a (meth) acrylic ester polymer.

  The hydrosilylation reaction is used for functional group conversion, crosslinking reaction, and the like, and is one of industrially very useful reactions. For example, a polymer having an alkenyl group as a functional group at the end of a molecular chain can be crosslinked and cured by using a hydrosilyl group-containing compound as a curing agent to give a cured product having excellent heat resistance and durability. It is known that a polymer having a crosslinkable silyl group at the terminal is produced by reacting a polymer having an alkenyl group at the terminal with a hydrosilyl group-containing compound having a crosslinkable silyl group. These hydrosilylation reactions proceed by heating, but a hydrosilylation catalyst is added to advance the reaction more rapidly. Such hydrosilylation catalysts include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts. In particular, it is known that when a transition metal catalyst is used, hydrosilylation can be rapidly advanced with a catalytic amount.

  We have recently developed (meth) acrylic acid ester-based alkenyl groups or crosslinkable silyl groups whose molecular weight and molecular weight distribution are controlled by using living radical polymerization (especially atom transfer radical polymerization), which is one of controlled polymerizations. A polymer and a curable composition using the polymer were successfully developed (Patent Documents 1 to 11).

  On the other hand, the (meth) acrylic acid ester polymer produced by using the atom transfer radical polymerization method, the polymerization catalyst residue acts as a catalyst poison of a hydrosilylation catalyst such as a transition metal catalyst, and the hydrosilylation reaction is remarkably performed. It is also known to inhibit. As a solution to this problem, we have developed an adsorption purification method (Patent Documents 12 to 17), and it is clear that it is particularly effective to use an acidic adsorbent such as aluminum silicate and a basic adsorbent such as hydrotalcite. (Patent Document 17).

  In addition, (meth) acrylic acid ester-based polymers having a crosslinkable silyl group obtained by using an atom transfer radical polymerization method include polymerization catalyst residues, initiator-derived acidic substances, hydrogen halides released from the polymer, etc. Due to the influence of the above, the crosslinking reaction is likely to proceed during production and storage, and so far, stabilization has been achieved by various methods. For example, a method of adding a dehydrating agent (or stabilizer) or the like (Patent Documents 18 and 19), a method of removing the halogen group of the polymer and stabilizing the polymer itself (Patent Documents 20 and 21), and the like can be mentioned. . However, it has been found that at the commercial production level, the storage stability may not be improved due to various factors such as the influence of impurities of raw materials and problems in manufacturing and storage.

Furthermore, in the polymer, an aromatic compound such as toluene or xylene is usually used as a solvent during the production process. This is because these solvents have a high property of dissolving the polymer and are inexpensive. However, there is a social demand to use a solvent instead of an aromatic compound due to environmental problems such as the sick house problem and the reduction of the environmental load inside the semiconductor clean room (Patent Document 22).
JP 09-272714 A Japanese Patent Laid-Open No. 11-80571 JP 09-272715 A Japanese Patent Laid-Open No. 11-5815 JP-A-11-80249 Japanese Patent Laid-Open No. 11-80250 JP-A-11-116617 Japanese Patent Laid-Open No. 11-116763 JP-A-11-130931 JP 2000-38404 A JP 2000-44626 A JP-A-11-193307 JP 2001-323011 A JP 2001-323012 A JP 2001-323016 A JP 2001-330221 A JP 2003-96130 A JP 11-43512 A JP 2004-51726 A JP 2000-344831 A JP 2003-292531 A JP 2003-96106 A

  The present invention suppresses hydrolysis of acetate ester while ensuring the purity of the polymer when performing high-temperature adsorption treatment of (meth) acrylic acid ester polymer using acetate ester, which is a non-aromatic compound, as a solvent. The present invention provides an economical and efficient method for producing a (meth) acrylic acid ester polymer.

  Acetic acid ester is used instead of the aromatic compound as a solvent, and the (meth) acrylic acid ester polymer is purified by adsorption at a temperature of 150 ° C. or higher. As the adsorbent, aluminum silicate and hydrotalcite are used in combination, and the amount of aluminum silicate used is 0.05 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the polymer.

  It exhibits the same degree of purification and hydrosilylation activity as conventional products obtained using aromatic compounds. In addition, deterioration of the acetic acid ester as a solvent is suppressed, and the solvent can be reused. Furthermore, acidification (increase in acid value) of the polymer can be suppressed, and as a result, the storage stability of the (meth) acrylic acid ester polymer having a crosslinkable silyl group can be improved.

  The present invention relates to a high-temperature adsorption treatment of a (meth) acrylic acid ester polymer using an acetate ester as a solvent. In order to obtain a desired degree of purification, the present invention is carried out in combination with other purification methods other than the present invention. May be. Although not described in detail as other purification methods, conventionally known methods may be used.

  The present invention was developed mainly for the expression of hydrosilylation activity for (meth) acrylic acid ester polymers produced by atom transfer radical polymerization, particularly polymers having alkenyl groups. Since there are effects such as suppression of deterioration and improvement of storage stability, the object is not limited to (meth) acrylic acid ester-based polymers produced by atom transfer radical polymerization, but conventionally known methods such as free radical polymerization Various (meth) acrylic acid ester polymers produced by the above method may be used. For the same reason, there may be no alkenyl group, and the functional group is not particularly limited to an alkenyl group as long as it can withstand high-temperature adsorption treatment, and may have a known functional group other than an alkenyl group.

  Since the (meth) acrylic acid ester polymer produced by atom transfer radical polymerization is technically difficult to remove the polymerization catalyst, preliminary purification (rough purification) is performed before the adsorption purification of the present invention. It is preferable to do. The preliminary purification method is not particularly limited, and a conventionally known method may be used. However, it is preferable to use a non-aqueous purification method such as an adsorption purification method as in the present invention, and it is aroma free in accordance with the spirit of the present invention. It is more preferable to use a simple purification method.

<Adsorption purification method>
First, the adsorption purification method will be described in detail. The adsorption system may be either a batch system or a continuous system such as an adsorption tower, but a batch system in which it is diluted with a solvent and an adsorbent is added and stirred is simple. The same applies to the case where preliminary purification is performed.

<Solvent during adsorption purification>
As the solvent for adsorption, a non-aromatic compound is used from the standpoint of environment, but generally a low polarity solvent is preferred because the adsorption ability is lowered when a highly polar solvent is used. The solvent used as the solvent is preferably an acetate ester in consideration of the adsorption ability and the solubility of the (meth) acrylic acid ester polymer, and butyl acetate is particularly preferred. The same applies to the case where preliminary purification is performed, but there is no particular limitation.

  The amount of solvent is not particularly limited, and can be adjusted according to the viscosity (monomer type, molecular weight / molecular weight distribution) of the polymer, the processing temperature, the amount of adsorbent, and the like. In general, it is preferably at least 1 part by weight, more preferably at least 5 parts by weight, even more preferably at least 50 parts by weight, particularly preferably at least 70 parts by weight, preferably at least 500 parts by weight per 100 parts by weight of the polymer. Parts or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less, and particularly preferably 150 parts by weight or less. In addition, when performing adsorption treatment in a batch system, it is necessary to remove the adsorbent by centrifugal sedimentation or filtration after the adsorption treatment, but additional solvent is added after the adsorption treatment to remove adsorbents such as centrifugal sedimentation or filtration. Removal may be performed. For example, when the adsorption temperature or filtration temperature is less than 160 ° C., the amount of solvent is preferably 70 to 150 parts by weight. When the adsorption temperature or filtration temperature is 160 ° C. or higher, the viscosity of the polymer also decreases, so the amount of solvent may be small, preferably 5 to 70 parts by weight, more preferably 5 to 30 parts by weight. . The same applies to the case where preliminary purification is performed, but there is no particular limitation.

<About adsorbent>
Examples of the adsorbent include synthetic resin adsorbents such as activated carbon and ion exchange resins, and inorganic adsorbents such as zeolite. In the present invention, an aluminum silicate and a hydrotalcite compound described later are used in combination. Aluminum silicates and hydrotalcite compounds are classified as inorganic adsorbents. Inorganic adsorbents generally have a solid acid and a solid base, and the particles have a porous structure, so the adsorbing ability is very high. Another feature is that it can be used from a low temperature to a high temperature.

  Aluminum silicate is obtained by replacing a part of silicon of silicic acid with aluminum, and pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth and the like are known. Among these, synthetic aluminum silicate has a large specific surface area and high adsorption capacity. Examples of the synthetic aluminum silicate include, but are not limited to, the Kyoward 700 series (manufactured by Kyowa Chemical).

Hydrotalcite compounds include divalent metals (Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^2+, etc.) and trivalent metals (Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , In ³⁺ +, etc.) or a part of the hydroxyl group of the hydroxide is a halogen ion, NO ³⁻ , CO ₃ ²⁻ , SO ₄ ^{2 -} , Fe (CN) ₆ ³⁻ , CH ₃ CO ²⁻ , oxalate ion, salicylate ion and other anions. Of these, hydrotalcites in which the divalent metal is Mg ²⁺ and the trivalent metal is Al ³⁺ and a part of the hydroxyl group is replaced with CO ₃ ²⁻ are preferable. Examples include, but are not limited to, the Ward 500 series and the Kyoto Ward 1000 series (both manufactured by Kyowa Chemical Co., Ltd.). An adsorbent obtained by firing the hydrotalcite is also preferably used. Among them, MgO—AlO ₃ solid solution obtained by firing hydrotalcites in which the divalent metal is Mg ²⁺ and the trivalent metal is Al ³⁺ is preferable, for example, Kyoward 2000 (Kyowa Chemical Co., Ltd.). )) And the like, but is not limited thereto. In the present invention, the fired hydrotalcite is also classified as hydrotalcite.

  Also in the case of performing preliminary purification, it is preferable to use aluminum silicate and a hydrotalcite compound in combination, but there is no particular limitation, and a conventionally known adsorbent may be used. For example, silicon dioxide; magnesium oxide; silica gel; silica / alumina; magnesium silicate; activated alumina; aluminum hydroxide; clay-based adsorbent such as acid clay and activated clay; and a generic name for hydrous aluminosilicate minerals such as sodium aluminum silicate. Inorganic adsorbents such as zeolite adsorbents; dosonite compounds; Adsorbents may be used alone or in admixture of two or more.

<Adsorbent amount>
The amount of aluminum silicate used in the present invention is 0.05 to 0.5 parts by weight, preferably 0.5 to 0.2 parts by weight, based on 100 parts by weight of the polymer. .

  If the amount of aluminum silicate is too small, purification is poor and the desired sufficient hydrosilylation activity is not exhibited. If the amount of aluminum silicate is excessive, hydrolysis of the acetic acid ester is likely to proceed due to high temperature heating, and the amount of acetic acid and alcohol generated increases. Degradation of the acetate ester as a solvent leads to deterioration of the quality of the polymer and must be avoided. For example, acetic acid generated by hydrolysis has a strong affinity with a (meth) acrylic acid ester polymer, and it is difficult to completely remove it from the polymer. If acetic acid remains in the polymer, it may cause odors and ultimately act as a catalyst for the crosslinking reaction of (meth) acrylic acid ester-based polymers having a crosslinkable silyl group, resulting in thermal stability and storage stability. It may be a cause of decline. In addition, acetic acid ester, which is a solvent, is usually separated and recovered from the polymer and used again as a solvent for adsorption purification, so acetic acid and alcohol accumulate in the acetic acid ester as the number of reuse increases. It will be. When the amount of accumulation increases, the efficiency of adsorption purification decreases and the amount of acetic acid remaining in the polymer increases, so that regeneration of the solvent, disposal cost, etc. are required. Similarly, the side chain ester group of the (meth) acrylic acid ester polymer is easily hydrolyzed, and the polymer itself may be damaged. Like acetic acid and alcohol, the side chain ester group of (meth) acrylic acid ester polymer is hydrolyzed and converted to a carboxyl group, which also acts as a catalyst for crosslinking reaction, thermal stability and storage stability Since it may adversely affect sex and the like, it is not preferable.

  The amount of the hydrotalcite compound used is not particularly limited, but is preferably 0.05 parts by weight or more and 10 parts by weight or less, and 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight. More preferred. Use of a large amount of adsorbent is not preferable because the yield of the polymer is lowered. Further, the increase in the amount of the adsorbent leads to a longer filtration time and an increase in the amount of adsorbent discarded.

  There is no particular limitation on the amount of adsorbent for preliminary purification, but when the same conditions as in the present invention, that is, when aluminum silicate is used and high-temperature adsorption purification is performed with an acetate solvent, the aluminum silicate is the same as in the present invention. The amount is 0.05 to 0.5 parts by weight, preferably 0.5 to 0.2 parts by weight, based on 100 parts by weight of the polymer.

<Adsorption temperature>
The adsorption temperature of the present invention is 150 ° C. or higher, preferably 170 ° C. or higher, more preferably 190 ° C. or higher. The higher the temperature, the higher the purification level and the better the hydrosilylation activity. Also, it is easy to reduce the amount of adsorbent. The (meth) acrylic acid ester polymer is excellent in high temperature resistance, but if the temperature is too high, the deterioration of the polymer proceeds, so that it is preferably 230 ° C. or less, more preferably 200 ° C. or less.

  When aluminum silicate is present in acetic acid ester and heated at a high temperature, hydrolysis proceeds with moisture contained in the adsorbent without actively adding water, and acetic acid and alcohol are generated. On the other hand, even in the hydrotalcite compound, water is contained in the adsorbent, but the amount thereof is less than that of aluminum silicate, and the hydrotalcite adsorbs acidic substances, so that the amount of acetic acid generated tends to be suppressed. It is preferable to use together also in that aspect.

<About (meth) acrylic acid ester polymer>
The present invention relates to a high-temperature adsorption treatment of a (meth) acrylic acid ester-based polymer using an acetate ester as a solvent, and has various ripple effects such as aroma-free, suppression of solvent deterioration, and improvement of storage stability. It can also be used as an adsorption purification method for various (meth) acrylic acid ester polymers produced by a conventionally known method such as a free radical polymerization method. Among them, it is effective in the purification of (meth) acrylic acid ester polymers produced by atom transfer radical polymerization, particularly (meth) acrylic acid ester polymers having an alkenyl group. Hereinafter, the (meth) acrylic acid ester-based polymer having an alkenyl group will be described in detail.

  The number of alkenyl groups is not particularly limited, and is appropriately determined so as to obtain a desired elongation at break and curing rate of the cured product, but at least one, preferably 1.2 to 5, in one molecule of the polymer. Preferably, there are 1.4 to 3, particularly preferably 1.6 to 2.5. When the number of alkenyl groups contained in one molecule of the polymer is less than 1, the curability of the (meth) acrylate polymer having a crosslinkable silyl group obtained through a hydrosilylation reaction becomes insufficient, It becomes difficult to develop good rubber elastic behavior.

  The alkenyl group may be present at the end of the polymer molecular chain or may be present inside (side chain). When present at the end of the molecular chain, the molecular weight between the cross-linking points is increased, so that a rubber-like cured product having high elongation and low elastic modulus is easily obtained. The alkenyl group may be present at at least one end, preferably at both ends of the polymer molecular chain.

  There is no restriction | limiting in particular as a (meth) acrylic acid ester monomer which comprises a (meth) acrylic acid ester type polymer, A various thing can be used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acryl Isobutyl acid, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, (Meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid phenyl, (meta ) Toluyl acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid 3-methoxypropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate , Γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2-perfluoroethylethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid Diperfluoromethyl methyl, (meth) acrylic acid 2- Examples include perfluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, and the like. It is done. These may be used alone or a plurality of these may be copolymerized.

  Among the above (meth) acrylate monomers, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid -N-butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, -n-pentyl (meth) acrylate, -n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( (Meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (Meth) acrylic acid phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid-2-methyl Xylethyl, (meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate are preferred, methyl acrylate, acrylic acid Particularly preferred are ethyl, n-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and stearyl acrylate. The preferred monomer is preferably contained in a weight ratio of 40% or more, more preferably 60% or more, and particularly preferably 80% or more.

  Other monomers can be copolymerized with the (meth) acrylic acid ester monomer as required. Examples of other monomers include (meth) acrylic acid; styrene monomers such as styrene, vinyltoluene, and α-methylstyrene; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc. Vinyl esters of the above; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like.

  When copolymerizing other monomers, it is preferable that the other monomers are contained in an amount of less than 40%, more preferably less than 20%, more preferably less than 10%. It is particularly preferable.

  The number average molecular weight of the (meth) acrylic acid ester-based polymer having an alkenyl group is not particularly limited, but the lower limit is preferably 3,000 or more, more preferably 5,000 or more, and the upper limit is preferably 100,000. Below, more preferably 50,000 or less. That is, 3,000-100,000 are preferable and 5,000-50,000 are more preferable. The molecular weight distribution of the polymer, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7. Is less than 1.5, more preferably less than 1.5, and particularly preferably less than 1.3. The molecular weight and molecular weight distribution in the present invention are measured by gel permeation chromatography (GPC). Usually, chloroform is used as the mobile phase, and the measurement is performed with a polystyrene gel column. It can be obtained by conversion.

<Atom transfer radical polymerization>
The atom transfer radical polymerization method is one of living radical polymerization methods, and radicals such as (meth) acrylic acid ester monomers using organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts. This is a method for controlling polymerization of a polymerizable monomer. Examples of the atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614. As a method for producing a (meth) acrylic acid ester-based polymer having an alkenyl group or a crosslinkable silyl group using atom transfer radical polymerization, the method disclosed in the literature (Patent Documents 1 to 22) already exemplified is referred to However, it is not limited to these.

  For example, when an organic halide is used as an initiator, the polymer terminal becomes a halogen group, and a functional group conversion reaction is likely to occur. It is also preferable to use a commercially available catalyst (for example, a complex of copper halide having pentamethyldiethylenetriamine or the like as a ligand) that is relatively inexpensive.

<Method of introducing alkenyl group into polymer>
There are various methods for introducing the alkenyl group into the (meth) acrylic acid ester-based polymer, and 1,5 at the end of the atom transfer radical polymerization of the (meth) acrylic acid ester monomer. A method of reacting a compound having a plurality of alkenyl groups such as -hexanediene, 1,7-octadiene, 1,9-decadiene is preferred.

  When carrying out preliminary purification, it is preferably carried out after the above-mentioned “method for introducing an alkenyl group into a polymer”.

<Halogen group elimination treatment method>
There are various methods for introducing the alkenyl group into the (meth) acrylic acid ester-based polymer, and there are a plurality of methods such as 1,5-hexanediene, 1,7-octadiene, 1,9-decadiene, etc. In the method of reacting a compound having an alkenyl group, a polymer obtained is obtained by adding a polymerization-active terminal halogen group to one of a plurality of alkenyl groups in the molecule such as 1,5-hexanediene. It is in a stopped state (α-haloester structure state), and a halogen group is still present at the end of the polymer. If the halogen group remains, it is liberated and an acid is generated, which causes corrosion of the substrate.

  The halogen group elimination treatment method includes, for example, a nucleophilic substitution reaction with a nucleophilic agent such as a carboxylate, a heating or elimination reaction with a base, and the like. By performing the heat treatment at a high temperature, an intramolecular cyclization reaction (formation of a lactone ring) involving an ester group adjacent to the halogen group proceeds, the alkyl halogen is eliminated, and the halogen group is removed. The high temperature heat treatment method may be performed by heating the polymer to a high temperature, but is preferably 120 ° C to 250 ° C, more preferably 150 ° C to 230 ° C, and particularly preferably 170 ° C to 200 ° C. In the case of volatile alkyl halogen, it can be heat-treated while being removed from the system by devolatilization.

  In addition, if the removal of the polymerization catalyst is inadequate and a high-polarity solvent is used during the halogen group treatment, or if high-temperature heating is performed, the polymerization catalyst will dissolve in the polymer, and the polymer will not be purified. Since it becomes difficult, it is preferable to carry out the above-mentioned preliminary purification before carrying out the “halogen group elimination treatment”. As the achievement level of the preliminary purification, the amount of residual catalyst is preferably 500 ppm or less, more preferably 200 ppm, particularly preferably 100 ppm or less with respect to the polymer as a metal amount.

  The (meth) acrylic acid ester polymer from which the halogen group has been eliminated is subjected to the adsorption purification treatment of the present invention to obtain the desired (meth) acrylic acid ester polymer.

  When the preliminary purification level is insufficient, the high temperature heat treatment in the presence of the adsorbent can suppress the dissolution of the polymerization catalyst into the polymer. Part or all of the adsorbent used in the process can be added in advance during the high-temperature heat treatment process. The adsorbent is preferably an inorganic adsorbent, more preferably an aluminum silicate or a hydrotalcite compound, and particularly preferably used in combination.

  When adding the adsorbent during the high-temperature heat treatment, it is preferable to carry out the adsorption purification of the present invention without filtering the adsorbent. In this case, since the adsorbent used during the high-temperature heat treatment is used as a part or all of the adsorbent used in the adsorption purification treatment according to the present invention, aluminum used during the high-temperature heat treatment and the adsorption treatment is used. The total amount of silicate is 0.05 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the polymer.

<About hydrosilylation reaction>
By purifying the (meth) acrylic acid ester polymer by the adsorption purification method of the present invention, the catalyst poison of the hydrosilylation reaction can be efficiently removed. As a result, it is possible to hydrosilylate the (meth) acrylic acid ester polymer. For example, an Si-H group-containing compound having a crosslinkable silyl group is converted to an alkenyl of the (meth) acrylic acid ester polymer. By adding to the carbon-carbon double bond of the group, a crosslinkable silyl group can be introduced at the end of the polymer. Examples of the crosslinkable silyl group include, but are not limited to, those represented by the following general formula.

_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a
(Wherein, R ^1, R ² represents an alkyl group containing 1 to 20 carbon atoms, an aryl group, an aralkyl group, _{or, (R ') 3 SiO- (} R' is hydrocarbon monovalent C1-20 A hydrogen group, and three R's may be the same or different), and when two or more R ¹ or R ² are present, Y may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. , 1, 2 or 3, and b represents 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 is satisfied.

  The hydrolyzable group represented by Y is not particularly limited, and conventionally known ones can be used. Specifically, hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group can be used. , An aminooxy group, a mercapto group, an alkenyloxy group, and the like, and an alkoxy group is particularly preferable from the viewpoint that it is mild and easy to handle. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + mb, that is, the total sum of hydrolyzable groups is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more. In the case of silicon atoms linked by a siloxane bond, up to about 20 silicon atoms may be used.

Specific examples of R ¹ and R ² include, for example, alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, and R ′ is a methyl group. and a phenyl group (R ') ₃ triorganosilyl group represented by SiO- and the like.
Among these crosslinkable silyl groups, those represented by the following general formula are particularly preferable.

-Si (R ² ) _3-a (Y) _a
(In the formula, R ² and Y are the same as described above. A is an integer of 1 to ^3. )
Specific examples include —SiCl ₃ , —Si (CH ₃ ) Cl ₂ , —Si (CH ₃ ) ₂ Cl, —Si (OCH ₃ ) ₃ , —Si (CH ₃ ) (OCH ₃ ) ₂ , —Si ( _{CH 3) 2 OCH 3, -Si} (OC 2 H 5) 3, -Si (CH 3) (OC 2 H 5) 2, -Si (CH 3) 2 OC 2 H 5, -Si (OC 3 H 7 ) ₃ , —Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , —Si (C ₂ H ₅ ) ₂ OCH ₃ , —Si (C ₆ H ₅ ) (OCH ₃ ) ₂ , —Si (C ₆ H ₅₎ ) ₂ (OCH ₃ ), —Si (CH ₃ ) (OC (O) CH ₃ ) ₂ , —Si (CH ₃ ) ₂ O— [Si (CH ₃ ) ₂ O] ₂ —Si (CH ₃ ) (OCH _{3) 2,} a _{-Si (CH 3) [O-} N = C (CH 3) 2] 2 ( where, in the above chemical formulas, C ₆ H ₅ represents a phenyl group).

  Although there is no restriction | limiting in particular as a Si-H group containing compound which has a silanol group or a hydrolyzable silyl group, The following are mentioned.

_{^{H- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a
(Wherein R ¹ , R ² , Y, a, m are the same as above)
In particular, the following are preferable from the viewpoint of easy availability.

H-Si (R ² ) _3-a (Y) _a
As a specific example,
_{HSiCl 3, HSi (CH 3)} Cl 2, HSi (CH 3) Cl 2,
HSi (OCH ₃ ) ₃ , HSi (CH ₃ ) (OCH ₃ ) ₂ , HSi (CH ₃ ) ₂ OCH ₃ , HSi (OC ₂ H ₅ ) ₃ , HSi (CH ₃ ) (OC ₂ H ₅ ) ₂ ,
HSi (CH ₃ ) ₂ OC ₂ H ₅ , HSi (OC ₃ H ₇ ) ₃ ,
HSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , HSi (C ₂ H ₅ ) ₂ OCH ₃ ,
HSi (C ₆ H ₅ ) (OCH ₃ ) ₂ , HSi (C ₆ H ₅ ) ₂ (OCH ₃ ),
HSi (CH ₃ ) (OC (O) CH ₃ ) ₂ ,
_{HSi (CH 3) 2 O- [} Si (CH 3) 2 O] 2 -Si (CH 3) (OCH 3) 2,
_{HSi (CH 3) [O-} N = C (CH 3) 2] 2
(However, in the above chemical formula, C ₆ H ₅ represents a phenyl group)
Etc.

  Examples of the hydrosilylated platinum catalyst used when adding such a hydrosilane compound having a crosslinkable silyl group to a (meth) acrylic polymer having an alkenyl group at the terminal include platinum alone, alumina, silica, carbon black, etc. In which platinum solid is dispersed in a carrier of the above, chloroplatinic acid, complexes of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin complexes, platinum (0) -1,1,3,3-tetramethyl- 1,3-divinyldisiloxane complex is mentioned, and platinum (0) -1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex is preferable because of its high activity. These catalysts may be used alone or in combination of two or more. The amount of the hydrosilylated platinum catalyst used is not particularly limited, but the amount of platinum metal is preferably in the range of 0.1 to 30 mg relative to 1 kg of the (meth) acrylic polymer having an alkenyl group at the end. It is more preferable that the reaction proceeds promptly and the range is 0.5 to 10 mg from the viewpoint of productivity improvement and economy.

  When a hydrosilane compound having a crosslinkable silyl group is added to a (meth) acrylic polymer having an alkenyl group at the terminal, for example, a hydrosilylated platinum catalyst is added to the (meth) acrylic polymer having an alkenyl group at the terminal May be added, and the hydrosilane compound having a crosslinkable silyl group may be dropped and dividedly added to cause the reaction, or the above components may be charged all at once and reacted.

  When a hydrosilane compound having a crosslinkable silyl group is added to a (meth) acrylic polymer having an alkenyl group at the terminal, it may or may not be in an inert gas atmosphere. In order to suppress consumption of the hydrosilane compound, it is preferable to be in a nitrogen atmosphere.

  When the hydrosilane compound having a crosslinkable silyl group is added to the (meth) acrylic polymer having an alkenyl group at the terminal, the reaction temperature is not particularly limited, but a range of 50 to 150 ° C. is preferable, and 70 to 120 A range of ° C is more preferred.

  When a hydrosilane compound having a crosslinkable silyl group is added to a (meth) acrylic polymer having an alkenyl group at the terminal, addition of a hydrolyzable ester compound and / or an alkyl alcohol will suppress gelation. Therefore, a hydrolyzable ester compound and / or an alkyl alcohol may or may not be added as necessary.

  Hydrolysable ester compounds include trialkyl orthoformate, triethyl orthoformate, tripropyl orthoformate, trialkyl orthoformate such as tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, etc. Examples are trialkyl acetates.

Other examples of hydrolyzable ester compound, wherein R _4-n SiY _n (wherein, Y is a hydrolyzable group, R represents be free also contain functional groups in a monovalent organic group N is an integer of 1 to 4, preferably 3 or 4, and specific examples thereof include methyltriethoxysilane, ethyltriethoxysilane, and phenyl. Triethoxysilane, methyltriacetoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, etc. Can be mentioned.

  0.1-50 weight part is preferable with respect to 100 weight part of (meth) acrylic-type polymers which have an alkenyl group at the terminal, and, as for the usage-amount of a hydrolysable ester compound, 0.1-30 weight part is more preferable.

  The alkyl alcohol is preferably an alcohol having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, hexanol, octanol and cellosolve. Etc. The alkyl alcohol is preferably used in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer having an alkenyl group at the terminal.

  The hydrolyzable ester compound and the alkyl alcohol may be used alone or in combination of two or more. Further, a hydrolyzable ester compound and an alkyl alcohol may be mixed and used.

  The hydrolyzable ester compound and / or alkyl alcohol has an effect of sufficiently suppressing gelation not only during the hydrosilylation reaction but also when added after the completion of the reaction.

<About curable composition>
The (meth) acrylic acid ester-based polymer having a crosslinkable silyl group obtained using the adsorption purification method of the present invention has a crosslinkable silyl group in which acidification of the polymer (an increase in acid value) is suppressed. Since the thermal stability and storage stability of (meth) acrylic acid ester-based polymers are improved, it can be used as a component of a curable composition as a polymer having better storage and handling than before. it can. Further, the improvement in storage stability of the (meth) acrylic acid ester polymer as a crosslinking component is nothing other than the improvement in storage stability of a curable composition using the same.

  Next, a curable composition containing a (meth) acrylic acid ester-based polymer having a crosslinkable silyl group will be described. In addition to the (meth) acrylic acid ester-based polymer having a crosslinkable silyl group, the curable composition can be used in combination with a conventionally known oxyalkylene polymer having a crosslinkable silyl group.

  The number average molecular weight (Mn) of the oxyalkylene polymer having a crosslinkable silyl group may be effectively 6,000 or more, preferably 6,000 to 60,000, more preferably 7,000 to 30,000.

  Molecular weight distribution (ratio of weight average molecular weight to number average molecular weight (Mw / Mn)) of the oxyalkylene polymer having a crosslinkable silyl group is 1.60 or less, further 1.50 or less, particularly 1.40 or less. When it is small, when compared with a polymer having the same molecular weight, the viscosity of the polymer or composition is lowered, and when used as a sealing material or an adhesive, workability such as extrudability and coating property is improved. Further, when Mw / Mn exceeds 1.60, further when 1.71 or more, 1.73 or more, 1.75 or more, particularly 1.80 or more, when compared with a polymer having the same molecular weight, The breaking strength of the cured product is improved.

  The mixing ratio of the (meth) acrylic acid ester-based polymer having a crosslinkable silyl group and the oxyalkylene polymer having a crosslinkable silyl group is not particularly limited, but the mixing ratio is preferably in the range of 1/99 to 99/1. Is more preferably in the range of 5/95 to 95/5. For example, the higher the mixing ratio of (meth) acrylic acid ester polymer (for example, 50/50 or more, 70/30 or more, or 90/10 or more in the mixing ratio) exhibits the effect of improving storage stability. In addition, when a cross-linkable silyl group of either (meth) acrylic acid ester polymer or oxyalkylene polymer or a trimethoxysilyl group having a high curing rate is present, the storage stability can be improved. Demonstrate.

  In curing the curable composition, a condensation catalyst may or may not be used. Condensation catalysts include titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin oxide and carboxylic acid ester or carboxylic acid Alternatively, a reaction product of a hydroxyl group-containing compound, an organic tin compound such as tin octylate and tin naphthenate; an organoaluminum compound such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetate Organic zirconium compounds such as natozirconium tetraisopropoxide and zirconium tetrabutoxide; Lead compounds: butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine , Amine compounds such as diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 or carboxylic acids thereof Salts; reactants and mixtures of amine-based compounds and organotin compounds such as laurylamine and tin octylate reactants or mixtures; excess polyamines and polybasic acids Low molecular weight polyamide resin obtained from the above; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxy What is necessary is just to use 1 type, or 2 or more types of well-known silanol catalysts, such as silane, as needed. The amount used is preferably in the range of 0 to 10 parts by weight with respect to the vinyl polymer having at least one crosslinkable silyl group. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because the curing rate is slow only with this polymer.

  Adhesion promoter, (meth) acrylic acid ester polymer itself has adhesion to glass, ceramics other than glass, metals, etc. Although it is possible to make it adhere, it is not always necessary, but it is preferably used in order to obtain stable adhesion to various substrates, parts, supports and adherends. Adhesion promoters include reaction of phenolic compounds such as phenol, cresol, xylenol, resorcinol, alkylphenol, and modified phenols (for example, cashew oil modified phenol and tall oil modified phenol) with aldehyde compounds such as formalin and paraformaldehyde. Resol type or novolak type phenolic resin obtained by the following: sulfur; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A type epoxy Epoxy resins such as resins; alkyl titanates such as tetrabutyl titanate, tolylene diisocyanate, diphenylmethane diisocyanate Any aromatic polyisocyanate; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- ( β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane and the like compounds having an amino group and a crosslinkable silyl group in one molecule; A compound having an epoxy group and a crosslinkable silyl group in one molecule such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc .; γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxy Compounds having a mercapto group and a crosslinkable silyl group in one molecule such as lan, γ-mercaptopropylmethyldimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyl A compound having an isocyanate group and a crosslinkable silyl group in one molecule such as methyldimethoxysilane; a compound having an amino group and a crosslinkable silyl group in one molecule as described above, and an epoxy group and a crosslinkable in one molecule A compound having a silyl group or a reaction product of a compound having an isocyanate group and a crosslinkable silyl group in one molecule; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- ( Such as meth) acryloxypropylmethyldimethoxysilane Such a reaction product of a compound having a (meth) acryloxy group and a crosslinkable silyl group in one molecule and a compound having an amino group and a crosslinkable silyl group in one molecule as described above. These may be used alone or in combination of two or more. Among them, compounds having amino groups and crosslinkable silyl groups in one molecule, compounds having epoxy groups and crosslinkable silyl groups in one molecule, mercapto groups and crosslinkable in one molecule, which are relatively easy to control physical properties and adhesiveness. Compound having silyl group, reaction product of compound having amino group and crosslinkable silyl group in one molecule and compound having epoxy group and crosslinkable silyl group in one molecule, (meth) acryloxy group and crosslinkable silyl group in one molecule Having a crosslinkable silyl group and an organic group having at least one of nitrogen, oxygen, and sulfur atoms in one molecule, such as a reaction product of a compound having an amino group and a crosslinkable silyl group in one molecule Compounds are preferred. Due to its high adhesiveness, the organic group having at least one of the above nitrogen, oxygen, and sulfur atoms is an amino group, an isocyanate group, or a group formed by a reaction thereof with nitrogen in one molecule. A compound having an organic group having an atom and a crosslinkable silyl group is more preferable.

  The adhesion promoter is preferably used in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer having at least one crosslinkable silyl group. If it is 0.01 part by weight, the effect of improving adhesiveness is hardly exhibited, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected. The addition amount of the adhesion promoter is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

  In order to control the physical properties by increasing the hardness when the adhesive curable composition is cured or decreasing the hardness to increase the physical properties, a physical property modifier can be used. Examples of the physical property modifier include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycol. Alkylisopropenoxysilanes such as sidoxypropylmethyldiisopropenoxysilane; various silane coupling agents such as vinyltrimethoxysilane and vinylmethyldimethoxysilane; silicone varnishes; polysiloxanes are added as required The A preferable result can be obtained by adding in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group. A curability modifier can be added to speed up or slow down the cure rate of the adhesive curable composition, and a storage stability modifier can be added to reduce thickening during storage. Curing modifiers or storage stability improvers include alcohols such as methanol and ethanol; orthoesters such as methyl orthoformate; and crosslinkable silyl groups such as tetraethoxysilane, methyltrimethoxysilane, and vinyltrimethoxysilane. Compound; Carboxylic acids such as 2-ethylhexanoic acid. A preferable result can be obtained by adding in an amount of 0 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymer having at least one crosslinkable silyl group.

  Other curable compositions include various fillers such as silica, carbon black and calcium carbonate; aromatic dibasic esters such as di (2-ethylhexyl) phthalate, and non-aromatic dibasic esters such as dioctyl adipate. Polyethers such as polypropylene glycol, various plasticizers such as acrylic oligomers, various solvents such as toluene and methyl ethyl ketone, various silane coupling agents, various modifiers such as polysiloxane having a crosslinkable silyl group, polyamide wax, hydrogenated Rheological property modifiers such as castor oil and metal soaps; surface property and / or weather resistance improvers such as UV curable resins and oxygen curable resins; colorants such as pigments and dyes; anti-aging agents, UV absorbers, light Additives such as stabilizers, flame retardants and the like may optionally be used.

  When the curable composition is used as a sealing material composition, fillers that can be added for the purpose of adjusting the mechanical properties are described in more detail. Fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, and carbon black. Reinforcing fillers such as calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon Materials: Fibrous fillers such as asbestos, glass fibers and filaments can be used. When you want to obtain a hardened product with high strength with these fillers, it is mainly fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc. A preferable result can be obtained by adding a filler selected from white and the like in an amount of 1 to 200 parts by weight per 100 parts by weight of the vinyl polymer having a crosslinkable silyl group. When it is desired to obtain a cured product having low strength and large elongation, a filler selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. A preferable result can be obtained by adding 1 to 200 parts by weight with respect to 100 parts by weight of the vinyl polymer having a group. These fillers may be used alone or in combination of two or more.

  Further, plasticizers that can be added to adjust the physical properties and viscosity are described in more detail. Phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate; dioctyl adipate, Non-aromatic dibasic acid esters such as dioctyl sebacate; polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; , Polypropylene glycol or polyethers obtained by converting these hydroxyl groups; chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl. Alone al, or they may be mixed and used two or more, do not necessarily need. These plasticizers can also be blended at the time of polymer production. When the amount of the plasticizer is added in the range of 0 to 100 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer having a crosslinkable silyl group, a preferable result is obtained. The sealing material composition of the present invention can be prepared as a one-component type that is cured by pre-blending and storing all the blended components in advance and absorbing moisture in the air after construction. Components such as a curing catalyst, a filler, a plasticizer, and water may be blended, and the blended material and the polymer composition may be adjusted as a two-component type that is mixed before use. The two-component type, which is often mixed with moisture or the like, further exhibits an effect of improving storage stability.

  When a curable composition is used as a pressure-sensitive adhesive composition, it is not always necessary to add a tackifying resin because it is mainly composed of a (meth) acrylic acid ester-based polymer. Can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.

  Solvents used for controlling workability are described in more detail. For example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve, methyl ethyl ketone, methyl isobutyl ketone And ketone solvents such as diisobutyl ketone. Those solvents may be used in the production of the polymer.

  The pressure-sensitive adhesive composition can be widely applied to tapes, sheets, labels, foils and the like. For example, solvent-type, emulsion-type, hot-melt type, etc. for substrate materials such as films made of synthetic resin or modified natural products, paper, all kinds of cloth, metal foil, metalized plastic foil, asbestos or glass fiber cloth The pressure-sensitive adhesive composition may be applied, exposed to moisture or moisture, and cured at room temperature or heat. It is also possible to use the curable composition as a high solid coating composition.

<About use of curable composition>
Applications of the curable composition include, but are not limited to, an elastic sealant for construction, a sealant for sizing boards, a sealant for double glazing, a sealant for vehicles, such as architectural and industrial sealants, and the back of solar cells Electrical and electronic parts materials such as sealants, electrical insulation materials such as insulation coatings for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, Paints, powder paints, coating materials, foams, sealing materials such as can lids, potting agents for electrical and electronic use, films, gaskets, casting materials, various molding materials, artificial marble, and meshed glass and laminated glass end faces ( Anti-rust / waterproof sealant for cutting parts), anti-vibration / vibration / soundproof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical parts, various machine parts Liquid sealing agent used in etc., it is available in a variety of applications such as waterproofing agents.

  A molded article exhibiting rubber elasticity obtained from the curable composition can be widely used mainly in gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors and the like as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  The curable composition is particularly useful as a sealing material and an adhesive, and is particularly useful for applications that require weather resistance and heat resistance and for applications that require transparency. Moreover, since a curable composition is excellent in a weather resistance and adhesiveness, it can be used for the exterior wall tile adhesion | attachment construction method without joint filling.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.

In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804, shodex GPC K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used. The functional group introduced per molecule of the polymer was subjected to functional group concentration analysis (solvent: deuterated chloroform, measurement temperature: 23 ° C.) by ¹ H-NMR (400 MHz), and calculated from the number average molecular weight determined by GPC.

  The amount of acid (acid value) was quantified by diluting the sample with isopropanol, performing potentiometric titration using a 0.1 N or 0.01 N KOH isopropanol solution, and determining the neutralization point.

<Reference Example 1>
New butyl acetate was heated to 190 ° C. in a sealed state and stirred for 2 hours. After cooling, the pH test paper was dipped in butyl acetate and was almost neutral.

<Reference Example 2>
0.1 parts by weight of water was added to 100 parts by weight of new butyl acetate, and the mixture was heated to 190 ° C. with only butyl acetate and water, and stirred for 2 hours. After cooling, the pH test paper was dipped in butyl acetate and was almost neutral.

<Reference Example 3>
The acid value of new butyl acetate was 2.3 KOH mmol / kg. Add 3 parts by weight of hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical Co., Ltd.) as an adsorbent to 100 parts by weight of new butyl acetate, and heat to 190 ° C under sealing with butyl acetate and adsorbent for 2 hours. Stir. After cooling, the adsorbent was filtered. When pH test paper was immersed in the filtrate butyl acetate, it showed acidity. When the acid value was measured, it was 11 KOH mmol / kg, and the acid value slightly increased.

<Reference Example 4>
The acid value of new butyl acetate was 2.3 KOH mmol / kg. Add 3 parts by weight of aluminum silicate (KYOWARD 700SEN: manufactured by Kyowa Chemical Co., Ltd.) as an adsorbent to 100 parts by weight of new butyl acetate, heat to 190 ° C in a sealed state with only butyl acetate and adsorbent, and stir for 2 hours did. After cooling, the adsorbent was filtered. When pH test paper was immersed in the filtrate butyl acetate, it showed acidity. When the acid value was measured, it was 180 KOH mmol / kg, and the acid value was significantly increased.

<Reference Example 5>
The acid value of new butyl acetate was 2.3 KOH mmol / kg. 3 parts by weight of hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical) and 3 parts by weight of aluminum silicate (KYOWARD 700SEN: manufactured by Kyowa Chemical) are added as adsorbent to 100 parts by weight of new butyl acetate. The mixture was heated to 190 ° C. in a sealed state with only the adsorbent and stirred for 2 hours. After cooling, the adsorbent was filtered and the acid value of butyl acetate as the filtrate was measured and found to be 125 KOH mmol / kg.

  As shown in Reference Examples 1 and 2, hydrolysis hardly progressed even when high-temperature heat treatment was performed in the presence of butyl acetate alone or a small amount of water, and acetic acid was not generated. As shown, when butyl acetate was heated at a high temperature in the presence of an adsorbent, hydrolysis proceeded, acetic acid was generated, and the acid value increased. In particular, it has been found that when aluminum silicate is used, the acid value increases remarkably, and excessive use of aluminum silicate causes an increase in acid value. It was also found that the combined use of hydrotalcite and aluminum silicate has the effect of suppressing the increase in acid value.

<Example 1>
Table 1 shows the amount of each raw material used.

(1) Polymerization process The inside of a stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester were charged and stirred under heating. Acetonitrile having a relative dielectric constant of 37.5 (20 ° C.) as a polymerization reaction solvent (described as “acetonitrile for polymerization” in Table 1) and diethyl 2,5-dibromoadipate as an initiator are added and mixed. At the stage adjusted to 80 ° C., pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature increases due to the heat of polymerization, so the internal temperature was adjusted to about 80 ° C to about 90 ° C. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, the unreacted monomer and acetonitrile for polymerization were removed by devolatilization under reduced pressure to obtain a polymer concentrate.

(2) Diene reaction step 1,7-octadiene (hereinafter abbreviated as diene or octadiene) and acetonitrile (described as diene reaction acetonitrile in Table 1) as a diene reaction solvent are added to the concentrate, and a triamine (diene in Table 1). The diene reaction was started by adding triamine for reaction). While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. The reaction solution was markedly colored by the polymerization catalyst used.

(3) Oxygen treatment step When the diene reaction was completed, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.

(4) First rough purification step As a non-aromatic hydrocarbon-based compound, butyl acetate ((dielectric constant 5.01 (20 ° C.)) was used as a diluent solvent for the polymer. The concentrate was diluted with about a part of butyl acetate, a filter aid was added and stirred, and then the insoluble catalyst component was removed by filtration, and the filtrate was colored and slightly turbid due to the polymerization catalyst residue.

(5) Second crude purification step The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and aluminum silicate (KYOWARD 700SEN: manufactured by Kyowa Chemical) and hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical) were added as adsorbents. . After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for 1 hour, insoluble components such as an adsorbent were removed by filtration. A clear filtrate with coloration was obtained. The filtrate was concentrated to obtain a crude polymer product.

(6) Dehalogenation process (high-temperature heat treatment process) / Adsorption purification process Crude polymer product, heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), part of the adsorbent (KYOWARD 700SEN, KYOWARD) 500SH), heated under stirring under reduced pressure, and heated and stirred, heated and stirred for about several hours at a high temperature of about 170 ° C. to about 200 ° C., and evacuated under reduced pressure to eliminate the halogen group in the polymer. Adsorption purification was performed. Add the remaining adsorbent (KYOWARD 700SEN, KYOWARD 500SH) and add about 10 parts by weight of butyl acetate (new product: acid value 2.3 KOHmmol / kg) as a diluent solvent to the gas phase. Was mixed with an oxygen-nitrogen mixed gas atmosphere, and further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for several hours to continue the adsorption purification. The total amount of the adsorbent used in the dehalogenation process / adsorption purification process was 1.5 parts by weight of hydrotalcite and 0.15 parts by weight of aluminum silicate. The treatment liquid was further diluted with 90 parts by weight of butyl acetate (new product: acid value 2.3 KOH mmol / kg) with respect to the polymer, and filtered to remove the adsorbent. The filtrate was concentrated to collect butyl acetate as a dilution solvent, and a polymer having alkenyl groups at both ends was obtained. The acid value of butyl acetate used and recovered once was 4.4 KOHmmol / kg.

(7) Silylation step Polymer obtained by the above method, methyldimethoxysilane (DMS), methyl orthoformate (MOF), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyl A predetermined amount of (disiloxane) platinum complex catalyst in isopropanol solution: hereinafter referred to as platinum catalyst] was mixed and heated to about 100 ° C. with stirring. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain a polymer having methoxysilyl groups at both ends. Table 1 shows the number of silyl groups introduced per molecule of the obtained polymer, the molecular weight, and the molecular weight distribution.

<Comparative Example 1>
Table 1 shows the amount of each raw material used.
In Example 1, (1) to (5) and (7) were carried out in the same manner, and (6) was carried out in the same manner except for the amount of adsorbent. The total amount of the adsorbent used in the dehalogenation process / adsorption purification process was 2.0 parts by weight of hydrotalcite and 2.0 parts by weight of aluminum silicate. The acid value of the recovered butyl acetate was 24 KOH mmol / kg.

  When Example 1 and Comparative Example 1 are compared, by reducing the total amount of aluminum silicate in step (6) from 1 part by weight to 0.15 parts by weight, an increase in acid value is suppressed even in actual polymer production. It was confirmed that

<Example 2>
In Example 1, the steps (1) to (5) and (7) are carried out in the same manner, and the butyl acetate collected and used once is reused for the step (6), not new butyl acetate. (Recycled once). The recovery and use of butyl acetate in the step (6) was repeated, and the acid value of butyl acetate (recycled twice) that was used and recovered three times was measured and found to be 15 KOH mmol / kg. The acid value of butyl acetate (recycled 14 times) collected and used 15 times was 23 KOH mmol / kg.

<Comparative example 2>
In Comparative Example 1, the steps (1) to (5) and (7) were carried out in the same manner, and (6) was not reused with new butyl acetate, but reused butyl acetate collected once (recovered) 1 recycling). The recovery and use of butyl acetate in the step (6) was repeated, and the acid value of butyl acetate (recycled twice) collected and used three times was 40 KOHmmol / kg.

  Comparing Example 2 and Comparative Example 3, by reducing the amount of aluminum silicate in the step (6), acid accumulation and increase in acid value were suppressed even when butyl acetate was repeatedly used.

<Example 3>
A polymer having a methoxysilyl group at both ends produced by the method described in Example 1 and 100 parts by weight of water were mixed well with 0.1 part by weight of water, and after degassing, the viscosity was 23 ° C. Measured with A glass sample bottle was filled and sealed, and heated at 50 ° C. for 4 weeks. After cooling, the viscosity was measured at 23 ° C. When the change in viscosity before and after storage at 50 ° C. for 4 weeks was determined, the rate of increase in viscosity was 2%, indicating good storage stability and thermal stability.

<Example 4>
0.1 part by weight of water was mixed well with 100 parts by weight of the polymer having methoxysilyl groups at both ends produced by the method described in Example 2 (14 times of recycling of butyl acetate), After degassing, the viscosity was measured at 23 ° C. A glass sample bottle was filled and sealed, and heated at 50 ° C. for 4 weeks. After cooling, the viscosity was measured at 23 ° C. When the change in viscosity before and after storage at 50 ° C. for 4 weeks was determined, the rate of increase in viscosity was 7%, indicating good storage stability and thermal stability.

  As in Examples 3 and 4, the polymer having a methoxysilyl group produced by the adsorption purification of the present invention showed good storage stability and thermal stability.

Claims (2)

  When mixing (meth) acrylic acid ester polymer, aluminum silicate and hydrotalcite compound as adsorbent, and acetic acid ester as solvent, and performing high-temperature adsorption treatment at a temperature of 150 ° C or higher, the amount of aluminum silicate used is important. A method for producing a (meth) acrylic acid ester-based polymer, wherein the content is 0.05 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the coalescence.   The production method according to claim 1, wherein the solvent is butyl acetate.