JP4652453B2 - Method for producing curable polysiloxane composition for building - Google Patents

Description

  The present invention relates to a method for producing an architectural curable polysiloxane composition, and more particularly, an architectural curable polysiloxane composition that forms a cured product having a matte surface suitable as a sealing material used for windows of high-rise buildings and the like. The present invention relates to a method for manufacturing a product.

  The reflected light of the sun from the windows of high-rise buildings is a kind of environmental problem because it illuminates people in the building on the other side, pedestrians on the street, drivers, etc., and it also impairs the beauty of the building It has caused.

  Therefore, recently, the windows of high-rise buildings have been designed with anti-glare consideration.

  By the way, curable polysiloxane resin is used as a putty or sealing material for waterproofing and anticorrosion for building exteriors, especially window frame parts, but the cured product of conventional polysiloxane resin is glossy. There was a problem that it was very good, and until the surface was soiled, it reflected sunlight and dazzled nearby people, and also damaged the aesthetics of the building as a building.

  As described above, the polysiloxane composition conventionally used for building exteriors has a very good surface gloss of the cured product. Has caused problems such as dazzling the appearance and detracting from the beauty of the building.

  The present invention has been made to solve such a conventional problem. Until the surface naturally loses its luster, the surface of the cured product is matted with a substance that has migrated from the inside, thereby eliminating the above problem. It aims at providing the manufacturing method of the curable polysiloxane composition for buildings which eliminated.

The manufacturing method of the curable polysiloxane composition for building which forms the hardened | cured material of the matte surface of this invention contains at least two hydroxyl groups couple | bonded with the silicon atom in (a) (A) 1 molecule, 25 100 parts by weight of a polyorganosiloxane having a viscosity at 100 ° C. of 100 to 500,000 cP, and (B) an organosilane containing two or more ketoxime groups bonded to a silicon atom in one molecule and / or a partially hydrolyzed bond 1 to 30 parts by weight, (C) 1 to 50 parts by weight of finely divided silica, and (D) 0.01 to at least one compound selected from metal carboxylates , organotin compounds, organotitanium compounds and alkoxyaluminum compounds (B) dodecylamine (laurylamine) with respect to 100 parts by weight of a room temperature-curable polyorganosiloxane composition each containing 10 parts by weight, Kutadeshiruamin, those obtained by heating and melting at least one amine compound 0.01 to 3.0 parts by weight is selected from Dokoseniruamin added under moisture blocking, characterized by uniformly mixed while heating.

  Since the room temperature curable polyorganosiloxane composition obtained by the present invention is cured, the blended component (b) is poorly compatible with the polyorganosiloxane of the base polymer of the component (a). It bleeds over time and adheres, and evenly adheres to the surface to make the surface glossy.

  Therefore, even when used for the exterior of a building, there is no problem of reflecting sunlight to dazzle nearby people or detracting from the architectural beauty of the building.

  The curable polysiloxane composition of component (a) used in the present invention is a polysiloxane resin composition that is liquid or raw rubber-like before curing and is cured by room temperature or slight heating, ultraviolet irradiation, or the like. Anything is acceptable.

  More preferred is a condensation type which is a one-component room temperature curing type from the viewpoint of workability and curability.

  Moreover, the range with preferable number average molecular weight is 1000-1 million, More preferably, it is 5000-500,000 as a molecular weight of the polyorganosiloxane which is a base polymer of the curable polysiloxane composition of (a). When it is less than 1000, the elongation as a cured product is poor and the properties as a sealing material are poor, and when it exceeds 1,000,000, the viscosity of the composition increases and the workability is remarkably deteriorated.

  As a typical curable polysiloxane composition as component (a), (A) a polyorganopolymer containing at least two hydroxyl groups bonded to silicon atoms in one molecule and having a viscosity of 100 to 500,000 cP at 25 ° C. 100 parts by weight of siloxane, (B) 1-30 parts by weight of organosilane and / or its partially hydrolyzed bond containing two or more ketoxime groups bonded to silicon atoms in one molecule, (C) finely divided silica 1 A room temperature curable polyorganosiloxane composition comprising 50 parts by weight and (D) 0.01 to 10 parts by weight of a curing catalyst is exemplified.

  The polyorganosiloxane of the component (A) is a polyorganosiloxane that has been conventionally used as a base for a binding reaction type liquid polymer.

（ｎは正の整数、Ｒは１価有機基）で示されるものがより好ましい。 The polyorganosiloxane as component (A) usually needs to contain at least two hydroxyl groups bonded to silicon atoms in one molecule, and the cured composition has good mechanical properties. It is preferable that the silicon atom bonded to the hydroxyl group is at the end of the polyorganosiloxane, and the general formula:

Those represented by (n is a positive integer and R is a monovalent organic group) are more preferred.

  Examples of the organic group R bonded to the silicon atom of the polyorganosiloxane represented by the above formula include monovalent hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, vinyl group and phenyl group, and chloromethyl group And monovalent substituted hydrocarbon groups such as cyanoethyl group and 3,3,3-trifluoropropyl group. It is preferable that 85% or more of R is a methyl group because it has an appropriate curing speed, the fluidity before curing is easy to handle, and the physical properties after curing, especially the modulus is low. In view of easiness, it is best that all of R are methyl groups. However, when heat resistance or cold resistance is particularly required, it is desirable to use a phenyl group as a part of R. The range of n varies depending on the type of R and its molar ratio, but due to ease of handling, fluidity of the composition, physical properties after curing, etc., the viscosity of component (A) is 100 cP to 500,000 cP at 25 ° C. When R is all methyl groups, n corresponds to the range of about 20 to 3000. When the viscosity of the component (A) is less than 100 cP, it is difficult to obtain good physical properties due to low viscosity, and when it exceeds 500,000 cP, extrusion workability and curability tend to be deteriorated.

  Component (B) is a cross-linking agent for cross-linking component (A) to give a network structure. For this purpose, organosilane containing at least two ketoxime groups bonded to silicon atoms and its partial hydrolysis are used. Decomposed bonds are used. Examples of the organic group other than the ketoxime group bonded to the silicon atom include a monovalent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, and a phenyl group, a chloromethyl group, a cyanoethyl group, 3, 3 A monovalent substituted hydrocarbon group such as, 3-trifluoropropyl group is exemplified, and a methyl group, a phenyl group or a vinyl group is preferable since it gives an appropriate descending rate. Examples of such organosilanes include silane compounds such as methyltris (diethylketoxime) silane, methyltris (methylethylketoxime) silane, vinyltris (methylenalketoxime) silane, and phenyltris (diethylketoxime) silane, or partially hydrolyzed thereof. Decomposed and bound materials are exemplified. Component (B) is used in an amount of 1 to 30 parts by weight per 100 parts by weight of component (A). When the blending amount of component (B) is less than 1 part by weight, a cured product having excellent elasticity and mechanical properties cannot be obtained, and when it exceeds 30 parts by weight, the resulting cured product becomes brittle.

  The fine powder silica of component (C) is a reinforcing filler that gives mechanical strength to the cured rubber elastic body. Examples of such reinforcing fillers include fumed silica, calcined silica, precipitated silica, and those whose surfaces are siliconized with organochlorosilanes, polyorganosiloxanes, hexamethyldisilazane, and the like. This component (C) is used in an amount of 1 to 50 parts by weight, preferably 5 to 25 parts by weight per 100 parts by weight of the component (A). When the blending amount of the component (C) is less than 1 part by weight, sufficient mechanical strength cannot be obtained, and dripping cannot be prevented sufficiently. Moreover, when it exceeds 50 weight part, mixing will become difficult and a compound will become hard too much, for example, appropriate viscosity as a sealing material will no longer be obtained.

  The curing catalyst for component (D) accelerates the binding reaction between component (A) and component (B). Such curing catalysts include carboxylic acid metal salts such as iron octoate, cobalt octoate, manganese octoate, zinc octoate, tin naphthenate, tin caprylate, tin oleate: diptyltin diacetate, dibutyltin dioctoate, dibutyltin Organotin compounds such as dilaurate, diethyltin dioleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin, dioctyltin dilaurate; chitrabutyl titanate, tetra-2-ethylhexyl tetanaate, Organic titanates such as triethanolamine titanate, tetra (isopropenyloxy) titanate; organosiloxy titanium, β-carbonyl titanium, etc. Machine titanium compound; alkoxy aluminum compounds, and the like are exemplified. (D) component is used in 0.01-10 weight part with respect to 100 weight part of (A) component. When the amount of the curing catalyst exceeds 10 parts by weight, not only the curability becomes too low, but also adversely affects the mechanical properties of the cured sealing material.

  The curable polysiloxane composition of the component (a) in the present invention has the components (A) to (D) as basic components, and other known fillers, plasticizers, colorants, and the like as necessary. You may mix | blend various solvents, such as a heat-resistant improver, a flame retardance imparting agent, an ultraviolet absorber, antioxidant, a flame retardant, toluene, alcohol, etc. in the range which does not impair the effect of this invention.

  Examples of the plasticizer include phosphoric acid esters such as tributyl phosphate and tricresyl phosphate, phthalic acid esters such as dioctyl phthalate, fatty acid monobasic acid esters such as glycerol monooleate, dibutyl adipate, dioctyl adipate, and the like. And fatty acid dibasic acid esters. These may be used alone or in combination of two or more. By adding the plasticizer, the elongation property after curing is further enhanced, and a low modulus can be achieved.

  The amount of additional components other than the component (A) that can be blended in the component (a) is 90% by weight or less, preferably 80% by weight or less of the whole component (a).

  The component (b) used in the present invention is a low molecular weight organic compound having a number average molecular weight of 2000 or less, a polar part in a part of a solid at room temperature, and a mostly nonpolar part. In this low molecular weight organic compound, the ratio of polar sites (Y) such as hetero atoms and metal salts such as C—N and C—O to nonpolar sites (X) such as C—C bonds in one molecule is particularly low. It is desirable to be in the range.

(Y) / [(X) + (Y)] × 100 = 0.1-20 (% by weight)
More preferably, this value is in the range of 1 to 10% by weight. If this ratio is less than 0.1% by weight, the compatibility with the polysiloxane is remarkably deteriorated and the storage stability of the composition is lacking. Conversely, if it exceeds 20% by weight, the compatibility with the polysiloxane is improved and the silicone resin surface is improved. Does not shift to matt state. Moreover, even if it is liquid at room temperature, it will not be matted even if it moves to the surface.

  As such a compound, a solid alkyl compound or arylamine compound containing a polar site is suitable, and specific examples include fatty acids, alcohols, fatty acid esters, amine compounds, amide compounds, and the like.

  Such fatty acids include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, Examples of alcohol include cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, and melyl alcohol. Examples of fatty acid esters include stearic acid. Examples include butyl, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, and amine compounds include laurylamine, stearylamine, tribenzylamine, diphenyl And amide compounds include, for example, lauric acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N- Examples include oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, lauric acid diethanolamide, palmitic acid diethanolamide, myristic acid diethanolamide, capric acid diethanolamide, and the like.

  The amount of component (b) added to 100 parts by weight of component (a) is preferably 0.01 to 3.0 parts by weight, and more preferably 0.05 to 1.0 parts by weight. If the amount added is less than 0.01 parts by weight, the resin surface will not be matted, while if it exceeds 3.0 parts by weight, the amount transferred to the resin surface will increase and the surface will be whitened, and the adhesiveness will deteriorate. is there. In the present invention, when the component (a), for example, each of the components (A) to (D) described above and the component (b) and other optional components described above are blended and mixed, first, the base of the component (a) Blend the polymer (A) component polyorganosiloxane and the crosslinking agent (B) component organosilane and / or its partially hydrolyzed bond with a mixer, kneader, etc. under the blending ratio described above in advance. Blend and mix uniformly. This mixing is performed in a state where moisture is turned off. Next, the finely divided silica of component (C) as a reinforcing filler, the curing catalyst of component (D), the component (b), and the optional component described above as necessary are added to the mixture. Mix in a state where the refusal is turned off and mix evenly. In addition, the mixture of the component (A) and the component (B) in the component (a) is blended again for the purpose of adjusting the viscosity of the system after blending the fine powder silica of the component (C) with this mixture. You may make it do. Next, examples of the present invention will be described.

  Moisture 100 parts by weight of polydimethylsiloxane having both ends blocked with hydroxyl groups and a viscosity of 10,000 cP, 5 parts by weight of methyltris (methylethylketoxime) silane, and 0.5 parts by weight of N-aminoethyl-aminopropyltrimethoxysilane The mixture was uniformly mixed in a container that was cut off, and 15 parts by weight of treated powder obtained by surface treatment of fumed silica Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) with octamethylcyclotetrasiloxane and 0.25 parts by weight of carbon black were added. The mixture was mixed until uniform, and 0.03 part by weight of dibutyltin dilaurate was added and mixed until uniform to obtain polysiloxane composition A (component (a)).

  Further, octadecylamine or glass balloon shown in the table melted by heating in polysiloxane composition A in a container in which moisture was blocked was charged, mixed at 100 ° C. until uniform, and cooled to room temperature. The compositions of 1-6, Reference Examples 7-9 and Comparative Examples 1-7 were obtained.

  The characteristics of the obtained composition are shown in the following table together with the composition. In addition, the characteristics in the table, the preparation conditions of the cured product, etc. are as follows.

Extrudability: Measured according to JIS A1439. The smaller the value, the lighter the composition is extruded from the cartrich tube and the better the workability.

Example of making cured product (sheet-like) ・ Place a 2 mm thick mold made of Teflon (registered trademark) on the Teflon (registered trademark) plate so that the composition of the comparative example does not adhere, The obtained composition was filled so as not to contain bubbles, and the surface was flattened using a spatula. Thereafter, the sample was allowed to stand for 3 days at 20 ° C. and 60% RH to be cured, and a 150 mm × 300 mm × 2 mm sample was prepared. The resulting cured product was measured for rubber properties, glossiness, and brightness.

・ Rubber properties (tensile strength, elongation, hardness)
It measured based on JISK-6301.

Glossiness Based on JISZ-8741, 60 ° specular gloss was measured using a gloss meter IG-310 (Horiba Seisakusho). The smaller the value, the less gloss.

Lightness ΔL was measured using a lightness / color difference meter CR-221 (manufactured by Minolta Camera Co., Ltd.). The smaller the value, the blacker it will be.

The composition of Examples and Comparative Examples was applied in a 10 mm bead shape on a 50 mm × 50 mm glass plate whose adhesive surface had been washed with IPA, and allowed to stand and cured for 3 days at 20 ° C. and 60% RH. Then, it cut | incised into the interface of glass and hardened | cured material using the knife, and peeled by hand, and adhesiveness was confirmed. Moreover, (circle), (triangle | delta), and x in a table | surface have the following meaning.
◯: The cured product was pseudo-collected and destroyed.
Δ: Peeling and cohesive failure of the cured product were mixed.
X: Hardened | cured material peeled from glass.

  As is apparent from the above table, the curable polysiloxane composition for buildings obtained by the present invention has a matte surface without deteriorating the properties as a sealing material (especially extrudability as workability). Therefore, it is possible to prevent the reflection of the sun from the sealing material sealed on the window frame.

Claims (1)

(A) (A) 100 parts by weight of polyorganosiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule and having a viscosity at 25 ° C. of 100 to 500,000 cP, and (B) silicon atoms in one molecule 1 to 30 parts by weight of an organosilane containing two or more ketoxime groups bonded to and / or a partially hydrolyzed bond thereof, (C) 1 to 50 parts by weight of finely divided silica, and (D) a carboxylic acid metal salt , A room temperature-curable polyorganosiloxane composition containing 0.01 to 10 parts by weight of at least one compound selected from an organotin compound, an organic titanium compound, and an alkoxyaluminum compound, with respect to 100 parts by weight,
(B) A solution obtained by heating and melting 0.01 to 3.0 parts by weight of at least one amine compound selected from dodecylamine (laurylamine), octadecylamine, and dococenylamine is added under moisture blocking while heating. A method for producing a curable polysiloxane composition for building which forms a cured product having a matte surface, characterized by mixing uniformly.