JP4225613B2 - Heat-curing modified silicone composition - Google Patents

Description

【００１５】
表１中、
注１)鐘淵化学工業(株)製の分子中に加水分解性アルコキシ基を含有するポリアルキレンエーテル系主鎖骨格の変性ポリマー、「Ｓ−２０３」
注２)中心粒径約８μmの１,１２−ドデカンジアミン(融点７１℃)７６．９部と中心粒径約０．０２μmの超微粒子酸化チタン２３．１部を混合し、Ｈi−Ｘミキサー(日清エンジニアリング(株)製)にて複合化処理することにより、中心粒径約８μmの微粉体コーティングアミン１００部を得る。
注３)東京ファインケミカル(株)製の、ジオクチル錫マレイン酸塩ボリマー(m．p．９０℃)
【００１６】
【発明の効果】
表１の結果から、本発明組成物(実施例１,２)は、室温条件下で硬化が抑制されるが、加熱条件下で硬化反応を起こすことが認められる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat curable modified silicone composition, more specifically, a modified silicone polymer containing a hydrolyzable silyl group in the molecule and a specific amine compound, and a heat curable adhesive, sealing material, and coating material. The present invention relates to a thermosetting modified silicone composition useful as a method.
[0002]
[Prior art]
Modified silicone polymers containing hydrolyzable silyl groups in the molecule cause a crosslinking reaction by the formation of siloxane bonds in the presence of moisture (humidity) in the air, so moisture-curing type sealing materials and coating materials Used as a polymer component.
[0003]
[Structure of the invention]
As a result of diligent investigations on the expansion of the use of the modified silicone polymer, the present inventors fixed a specific proportion of fine powder on the surface of the solid amine and coated the surface with active amino groups. If a compound is added, curing is suppressed under room temperature conditions. For example, under the heating conditions of 80 to 140 ° C. × 10 minutes, active amino groups are generated by heating and melting the fine powder coating amine, and the curing reaction The present invention has been completed.
[0004]
That is, the present invention provides (A) a modified silicone polymer containing a hydrolyzable silyl group in the molecule, and
(B) On the surface of a solid amine having a melting point of 50 ° C. or more and a center particle size of 20 μm or less, a fine powder having a center particle size of 2 μm or less, and a weight ratio of the solid amine to the fine powder of 1 / 0.001 to 0.5 Thus, the present invention provides a heat-curable modified silicone composition comprising a finely powder coated amine coated with active amino groups on the surface.
[0005]
Examples of the modified silicone polymer as component (A) in the present invention include, for example, polyoxyalkylene ether, polyester, (meth) acrylic polymer, polyisobutylene and the like as a main chain skeleton, and a hydrolyzable group at the terminal or side chain. Examples thereof include liquid polymers having a silyl group or silanol group having a hydroxyl group, a halogen group, an alkoxy group, a mercapto group, or the like.
[0006]
As the solid amine in the present invention, any of aromatic or aliphatic compounds having a melting point of 50 ° C. or higher may be used. For example, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol O-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine Aromatics such as 1,12-dodecanediamine, 1,10-decanediamine, 1,8-octanediamine, 1,14-tetradecanedia , 1,16 aliphatic such as hexadecane diamine and the like, may be subjected to one kind of them or a mixture of two or more in use. The solid amine is adjusted to have a center particle size of 20 μm or less, preferably 3 to 15 μm. When the center particle diameter exceeds 20 μm, an incompletely reacted cured product tends to be obtained upon heat curing.
[0007]
In the present invention, the fine powder-coated amine which is the component (B) is obtained by pulverizing the solid amine to a predetermined central particle size range and simultaneously adding the fine powder to the predetermined fine particle size range. The mixture is pulverized and mixed so that the fine powder is fixed on the surface of the solid amine. In addition, a fine powder-coated amine can be produced by using a high-speed impact mixing stirrer or a compression shear mixing stirrer together with fine powder of a finely pulverized solid amine, and this method, particularly high-speed impact mixing stirrer. More preferably, a machine is used.
[0008]
The fine powder can be used arbitrarily from inorganic or organic, for example, titanium oxide, calcium carbonate, clay, silica, zirconia, carbon, alumina, talc, etc. Examples thereof include vinyl chloride, polyacrylic resin, polystyrene, and polyethylene, and one or a mixture of two or more thereof is used. The amount used is selected so that the weight ratio of solid amine to fine powder is 1 / 0.001 to 0.5, preferably 1 / 0.002 to 0.4. When the ratio of the fine powder is less than 0.001, the effect of storage stability is not recognized, and when it exceeds 0.5, the storage stability is not further improved.
By mixing and pulverizing the solid amine and fine powder in this way, static electricity is generated and the fine powder adheres to the surface of the solid amine, or the mechanical force of the mixing stirrer generates friction, impact, compression shear, etc. It is predicted that the fine powder will stick due to the local melting and sticking phenomenon of the solid amine due to the heat generated by the solid amine, or it will be physically thrown or buried firmly on the surface of the solid amine, or even chemically activated and stuck. (That is, the active amino group (NH ₂ ) on the surface of the solid amine is covered with the fine powder). It is important that the center particle size of the fixed fine powder is set to 2 μm or less, preferably 1 μm or less. If it exceeds 2 μm, the fine particle does not adhere to the surface of the solid amine.
[0009]
The amount of the fine powder coating amine (B) used is usually selected in the range of 0.1 to 20 parts with respect to 100 parts (parts by weight, the same applies hereinafter) of the modified silicone polymer. If it is less than 0.1 part, it cannot be cured for a short time by heating, and if it exceeds 20 parts, it is not economical.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The thermosetting modified silicone composition according to the present invention is composed of a system in which the above modified silicone polymer (A) and fine powder coating amine (B) are blended, and a filler (for example, heavy calcium carbonate, for example). , Calcium carbonate surface-treated with fatty acids, carbon black, silicic anhydride, clay, talc, fibrous materials, metal powder, etc.), solvents or diluents (for example, aliphatic hydrocarbons, aromatic carbonization as low polarity solvents) Hydrogen-based, alicyclic hydrocarbon-based, halogenated hydrocarbon-based, ethers, esters, ketones, etc., particularly aliphatic hydrocarbon-based solvents are preferable, plasticizers (for example, dibutyl phthalate, dioctyl phthalate) , Dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dibenzyl phthalate, butyl base Diphthalate, trioctyl phosphate, epoxy plasticizer, toluene-sulfoamide, chloroparaffin, adipic acid ester, castor oil, etc.) and other additives (e.g. chemical foaming agents, thixotropic agents, UV absorbers, anti-aging agents, An appropriate amount of at least one selected from the group of dyes and pigments, adhesion imparting agents, dehydrating agents and the like may be blended.
[0011]
Further, a heat curing catalyst having a melting point (mp) of 40 ° C. or higher, preferably 60 ° C. or higher may be blended.
As such a heat curing catalyst, for example,
(i) m. p. Powder or solid metal compound at room temperature of 40 ° C. or more, specifically dibutyltin distearate, dibutyltin maleate polymer, dibutyltin bis (maleic acid alkyl ester) salt [where alkyl includes butyl, octyl, etc. Exemplified, the same shall apply hereinafter), bis (dibutyltin maleic acid alkyl ester) maleate, dibutyltin s, o-mercaptocarboxylate polymer, dioctyltin distearate, dioctyltin maleate polymer, dioctyltin bis (maleic acid alkyl ester) ) Salt, bis (dioctyltin maleic acid alkyl ester) maleate, dioctyltin s, o-mercaptocarboxylate polymer, tetrastearyl titanate, acetylacetonate polytitanate, tetramethyl titanate, aluminum isopropylate, aluminum ethyl Rate, zirconium acetylacetonate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), polyhydroxy titanium stearate, etc .:
[0012]
(ii) m. p. Silanol curing catalyst (for example, dibutyltin dilaurate, etc.) microencapsulated in a polymer shell (for example, acrylonitrile-butadiene rubber, acrylic rubber, styrene-butadiene rubber, ethylene-vinyl acetate rubber, vinyl chloride resin, acrylic resin, etc.) at 40 ° C. or higher. Dibutyltin maleate, dibutyltin diacetate, tin carboxylates such as tin octylate, tin naphthenate, organoaluminum compounds such as isopropoxyaluminum ethyl acetate, chelate compounds such as dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, Titanates such as tetrabutyl titanate);
(iii) Examples of metal components include Sb, Pb, Sn, Al, Zr, Bi, Zn, Mg, Fe, Ti, etc., and carboxylates, ester compounds or oxides (oxides) of these metal components, or metals Form a chelate structure with the component m. p. Powder or solid metal compound at room temperature of 40 ° C. or more, specifically lithium stearate, magnesium stearate, zinc stearate, zinc laurate, zinc ricinoleate, dibutyltin oxide, dioctyltin oxide, polyacetyl titanate acetylacetate Nert, tetramethyl titanate, aluminum isopropylate, aluminum ethylate, zirconium acetylacetonate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), polyhydroxytitanium stearate, etc., selected from these groups At least one selected from these may be used. The amount used is usually 0.1 to 20 parts, preferably 0.5 to 10 parts, based on 100 parts of the modified silicone polymer. These heat curing catalysts contribute to the acceleration of thermosetting.
[0013]
【Example】
Next, an Example and a comparative example are given and this invention is demonstrated more concretely.
Examples 1 and 2 and Comparative Example 1
By blending the components shown in Table 1 below, various curable modified silicone compositions are obtained.
Each of these modified silicone compositions was applied to an electrodeposited steel sheet with a thickness of 2 mm, and then allowed to stand for 2 to 48 hours at 30 ° C. and 80% RH (moisture curing), or heat curing conditions ( The cured state at 120 ° C. × 30 minutes or 100 ° C. × 10 minutes) was examined, and the results are shown in Table 1.
[0014]
[Table 1]

[0015]
In Table 1,
Note 1) “S-203”, a modified polymer of a polyalkylene ether main chain skeleton containing a hydrolyzable alkoxy group in a molecule manufactured by Kaneka Chemical Co., Ltd.
Note 2) 76.9 parts of 1,12-dodecanediamine (melting point 71 ° C.) having a center particle size of about 8 μm and 23.1 parts of ultrafine titanium oxide having a center particle size of about 0.02 μm are mixed together, and a Hi-X mixer ( Compounding with Nisshin Engineering Co., Ltd., 100 parts of fine powder coated amine having a center particle size of about 8 μm is obtained.
Note 3) Dioctyltin maleate polymer (mp 90 ° C) manufactured by Tokyo Fine Chemical Co., Ltd.
[0016]
【The invention's effect】
From the results in Table 1, it can be seen that the compositions of the present invention (Examples 1 and 2) are cured under room temperature conditions but undergo a curing reaction under heating conditions.

Claims (2)

(A) a modified silicone polymer containing a hydrolyzable silyl group in the molecule, wherein the main chain skeleton is selected from polyoxyalkylene ethers, polyesters, (meth) acrylic polymers and polyisobutylenes, and
(B) On the surface of a solid amine having a melting point of 50 ° C. or more and a center particle size of 20 μm or less, a fine powder having a center particle size of 2 μm or less, and a weight ratio of the solid amine to the fine powder of 1 / 0.001 to 0.5 and anchored thereby so, Ri a fine powder coating amine coated with active amino groups of the surface formed,
Component (A) and the heating-curing modified silicone composition weight ratio and wherein the 100 / 0.1 to 20 der Rukoto component (B). In addition, a heat curing catalyst with a melting point of 40 ° C or higher ( A ) The thermosetting modified silicone composition according to claim 1, wherein 0.1 to 20 parts by weight is blended with 100 parts by weight.