JP5752661B2 - Organopolysiloxane composition - Google Patents

Description

  The present invention relates to an organopolysiloxane composition, in particular, a multi-component room temperature curable organopolysiloxane composition suitably used as a silicone-based sealant or an adhesive.

  Condensation-curable room temperature curable organopolysiloxane compositions are used in many fields as silicone-based sealants, adhesives, coating agents, potting agents, etc., and are generally divided into one-component and multi-component forms. Separated. In the one-component form, since the crosslinking reaction is caused by moisture in the air, the curing reaction proceeds gradually from the surface. On the other hand, multi-component forms such as two components do not require moisture in the air for the crosslinking reaction, and are excellent in deep part curability.

  Examples of the curing catalyst used in the condensation curable organopolysiloxane composition include lead, tin, zirconium, antimony, iron, cadmium, and the like as described in JP-A-48-37452 (Patent Document 1). Barium, calcium, titanium, lead, and manganese are known, and generally tin compounds and titanium compounds are used. However, the tin compound has a problem of toxicity and a problem that the main chain of the organopolysiloxane is cleaved by immersion in hot water to cause cracking, resulting in a decrease in hardness over time. Therefore, development of a multi-component room temperature curable organopolysiloxane composition that does not contain a tin compound is required.

  In addition, when a titanium compound is used as a catalyst for a multi-component room temperature curable organopolysiloxane composition, the composition gels after mixing, and the pot life is extremely short after mixing, resulting in an extremely short pot life. There is a problem that stickiness is generated on the surface of the cured product and a problem that the composition is not cured when thinly applied.

  JP-A-2003-119387 (Patent Document 2) describes a room temperature-curable organopolysiloxane composition that does not use a tin compound or a titanium compound, and describes that a bismuth compound-based curing catalyst is used. Yes. However, the composition has a problem that the surface of the cured product is sticky, and a problem that the composition does not cure when thinly applied.

  Japanese Unexamined Patent Application Publication No. 2009-292914 (Patent Document 3) describes a condensation curable organopolysiloxane composition using an amine functional silane compound as a catalyst instead of a metal atom-containing compound. However, the composition has a problem of poor durability.

  JP 2009-132797 A (Patent Document 4) discloses a cured product surface by using a curing catalyst comprising a bismuth compound-based curing catalyst and / or a titanium compound-based curing catalyst (titanium chelate compound) and an iron compound. It is described that it is effective for the problem of causing stickiness in the film and the problem that the composition does not cure when thinly applied.

JP-A-48-37452 JP 2003-119387 A JP 2009-292914 A JP 2009-132797 A

  However, when the present inventors used a curing catalyst in which a titanium compound and an iron compound were combined, the composition easily gelled after mixing, the viscosity immediately increased, and the pot life was very short. Therefore, it was not possible to obtain a pot life equivalent to or better than that of a composition using a tin compound. Moreover, the problem that stickiness remained on the hardened | cured material surface and the problem that the composition apply | coated thinly did not harden | cured also occurred. Furthermore, a new problem of coloring or discoloration occurred (Comparative Examples 7 and 8 of the present application).

  Further, curing of a multi-component room temperature curable silicone rubber composition using a titanium salt of a carboxylic acid such as titanium naphthenate or titanium octylate, which is known as a curing catalyst for a condensation curable room temperature curable organopolysiloxane composition. When used as a catalyst, the pot life was very short, and it was not possible to obtain pot life equal to or greater than that of a composition using a tin compound (Comparative Example 1 of the present application).

  The present invention has been made in view of the above circumstances, and firstly, without containing a tin compound, it is possible to obtain a pot life that is equal to or greater than that of a composition using a tin compound, and is curable. The object is to provide a multi-component room temperature curable organopolysiloxane composition which is good. Furthermore, the present invention provides a multi-component room temperature curable organopolysiloxane composition that does not cause stickiness on the surface of the cured product, has good thin film curability, little coloration or discoloration, and good durability. The purpose is to do.

  As a result of various studies, the present inventors have been able to have a long pot life without using a tin compound and to have good curability by using a combination of a carboxylic acid titanium salt and a carboxylic acid. It was found that a multi-component room temperature curable organopolysiloxane composition can be provided. Further, the present inventors have found that the cured product obtained from the composition has no stickiness on the surface, the composition has good thin film curability, little coloration or discoloration, and good durability. The present invention has been found and the present invention has been made.

That is, the present invention
(A) Diorganopolysiloxane having a hydroxyl group and / or a hydrolyzable group at both ends of the molecular chain and having a viscosity of 20 to 1,000,000 mPa · s at 25 ° C .: 100 parts by mass
10 to 100 parts by mass of 100 parts by mass of the component (A) is a diorganopolysiloxane having a hydroxysilyl group at both ends of the molecular chain.
(B) Silane compound and / or siloxane having 3 or more alkoxy groups bonded to silicon atoms in the molecule (provided that the component (B) is different from the component (A)): 0.1 to 40 parts by mass ,
(C) One type selected from a monovalent carboxylic acid titanium salt having a saturated hydrocarbon group having 6 to 18 carbon atoms and a monovalent carboxylic acid titanium salt having an unsaturated hydrocarbon group having 6 to 21 carbon atoms Or 2 or more types : 0.001 to 20 parts by mass, and (D) 1 having a monovalent carboxylic acid having a saturated hydrocarbon group having 6 to 18 carbon atoms and an unsaturated hydrocarbon group having 6 to 21 carbon atoms One or more selected from polyvalent carboxylic acids: The organopolysiloxane composition containing 0.001 to 20 parts by mass and containing no iron compound is provided.

  When the organopolysiloxane composition of the present invention contains a combination of a carboxylic acid titanium salt and a carboxylic acid, it can achieve a long pot life equivalent to or longer than that of a composition containing a tin compound. The organopolysiloxane composition of the present invention is excellent in surface curability, thin film curability, internal curability, and storage stability, and does not cause coloring or discoloration. Therefore, according to the present invention, a multi-component room temperature curable organopolysiloxane composition having a long pot life and good curability can be provided without using a tin compound. . Therefore, the organopolysiloxane composition of the present invention is useful as a sealing material, an adhesive, a coating agent, or a potting agent. In particular, since the organopolysiloxane composition of the present invention is excellent in deep part curability and can be applied to deep joints and has good adhesion and durability, the composition is used as a sealing material for construction and civil engineering applications. If it is used, it becomes possible to maintain the waterproof function etc. which are the main objectives of a sealing material over a long period of time.

Hereinafter, the present invention will be described in detail.

[(A) component]
Component (A) is a diorganopolysiloxane having a hydroxyl group and / or a hydrolyzable group at both ends of the molecular chain, and is the main component of the organopolysiloxane composition of the present invention. The molecular structure of the diorganopolysiloxane is not particularly limited, and may be any of linear, branched, and linear having a branched structure, but is preferably linear. The linear diorganopolysiloxane may have a small amount of a branched structure. The diorganopolysiloxane may have a silmethylene structure (-SiRSi-) in the molecular chain. In the above formula, R is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. In addition, part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom or a cyano group.

  The diorganopolysiloxane has a viscosity at 25 ° C. of 20 to 1,000,000 mPa · s, preferably 100 to 300,000 mPa · s, more preferably 1,000 to 200,000 mPa · s, particularly 10,000 to It should have 100,000 mPa · s. If the viscosity of the diorganopolysiloxane is less than the above lower limit, a large amount of the component (B) described later is required, which is economically disadvantageous. Further, if the viscosity of the diorganopolysiloxane exceeds the above upper limit, workability is lowered, which is not preferable. In the present invention, the viscosity is a value measured by a rotational viscometer (hereinafter the same).

  The hydrolyzable group is preferably an alkoxy group or an alkoxyalkoxy group. The number of hydroxyl groups and hydrolyzable groups present at each end of the diorganopolysiloxane is not particularly limited. Preferably, when having a hydroxyl group at the terminal, it is preferable to have one hydroxyl group (that is, a hydroxysilyl group) bonded to a silicon atom at each terminal of the molecular chain. Further, when having an alkoxy group or an alkoxyalkoxy group at the terminal, an alkoxy group bonded to a silicon atom (that is, alkoxysilyl group) or an alkoxyalkoxy group bonded to a silicon atom (that is, alkoxyalkoxy group) at both ends of the molecular chain. It is preferable to have two or three silyl groups).

  The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. The alkoxyalkoxy group is preferably an alkoxyalkyl group having 2 to 10 carbon atoms, and examples thereof include a methoxymethoxy group, a methoxyethoxy group, and an ethoxymethoxy group. In particular, it is preferable that both ends of the diorganopolysiloxane are a hydroxyl group, a methoxy group, or an ethoxy group.

  Examples of the organic group bonded to the silicon atom other than the hydroxyl group and the hydrolyzable group include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group. Aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; some or all of the hydrogen atoms bonded to carbon atoms of these groups are fluorine, bromine, Examples substituted by halogen atoms such as chlorine or cyano groups, such as halogenated monovalent hydrocarbon groups such as trifluoropropyl group and chloropropyl group; cyanoalkyl groups such as β-cyanoethyl group and γ-cyanopropyl group Is done. Of these, a methyl group is preferred.

As the (A) diorganopolysiloxane, a compound represented by the following general formula (1) is particularly preferable.

In the above formula (1), R ^{1 s} are independently of each other a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; a methoxymethyl group, a methoxy group It is a group selected from an alkoxyalkyl group having 2 to 10 carbon atoms such as an ethyl group and an ethoxymethyl group. Preferably, they are a hydrogen atom, a methyl group, or an ethyl group. R ² is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include organic groups other than the hydroxyl groups and hydrolyzable groups described above, and among them, a methyl group is preferable. a is 0, 1 or 2. In particular, when R ¹ is an alkyl group or an alkoxyalkyl group, a is 0 or 1, and when R ¹ is a hydrogen atom, a is preferably 2. n is a viscosity of the diorganopolysiloxane at 25 ° C. of 20 to 1,000,000 mPa · s, preferably 100 to 300,000 mPa · s, more preferably 1,000 to 200,000 mPa · s, particularly 10 The number is in the range of 1,000 to 100,000 mPa · s.

式（２）中、Ｒ^２は上記の通りであり、Ｚは炭素原子数１〜２０、好ましくは炭素原子数１〜６の、非置換又は置換の二価炭化水素基である。 In the above formula (1), Y is independently of each other an oxygen atom, an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, or the following general formula (2 ).

In Formula (2), R ² is as described above, and Z is an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.

  The divalent hydrocarbon group may be linear or have a branched structure. In particular, a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group is preferable. Among these, an ethylene group is particularly preferable.

The diorganopolysiloxane can be produced by a conventionally known method. These diorganopolysiloxanes may be used singly or in combination of two or more. In particular, diorganopolysiloxane having a hydroxysilyl group at both ends of the molecular chain (that is, diorganopolysiloxane in which R ^{1 at} both ends in the above formula (1) is a hydrogen atom) is added in 100 parts by mass of component (A). It is preferable to contain in the quantity used as 10-100 mass parts, and it is still more preferable to contain in the quantity used as 50-100 mass parts.

[Component (B)]
The component (B) is a silane compound and / or siloxane having 3 or more hydrolyzable groups bonded to silicon atoms in the molecule. Component (B) undergoes a condensation reaction with component (A) to form a crosslinked structure. However, in the present invention, the component (B) is a compound different from the component (A).

  Examples of the hydrolyzable group include alkoxy groups, alkoxyalkoxy groups, acyloxy groups, alkenoxy groups, ketoxime groups, aminoxy groups, and amide groups having 1 to 10 carbon atoms. For example, alkoxy groups such as methoxy group, ethoxy group and propoxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group and methoxypropoxy group; acyloxy groups such as acetoxy group and octanoyloxy group; vinyloxy group, isopropenoxy group, Alkenoxy groups such as 1-ethyl-2-methylvinyloxy group; ketoxime groups such as dimethyl ketoxime group, methyl ethyl ketoxime group and methyl isobutyl ketoxime group; aminoxy groups such as dimethylaminoxy group and diethylaminoxy group; N-methyl Amide groups such as an acetamide group and an N-ethylacetamide group can be mentioned. Among these, an alkoxy group and a ketoxime group are preferable, and an alkoxy group is particularly preferable.

  Examples of the organic group bonded to the silicon atom other than the hydrolyzable group include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an octadecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group; Alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups such as benzyl group, phenethyl group, and phenylpropyl group; hydrogen bonded to carbon atoms of these groups What substituted a part or all of atoms by halogen atoms, such as fluorine, bromine, and chlorine, or a cyano group, for example, halogenated alkyl groups, such as 3-chloropropyl group and 3,3,3-trifluoropropyl group, etc. Can be mentioned. Of these, a methyl group, an ethyl group, a propyl group, a vinyl group, and a phenyl group are preferable.

  Examples of the silane compound include methyltrimethoxysilane, ethyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxy. Alkoxysilanes such as silane, tetramethoxysilane, tetraethoxysilane, methyltris (dimethylketoxime) silane, methyltris (methylethylketoxime) silane, ethyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane, vinyltris (methylethylketoxime) Ketoxime silanes such as silane; methyltri (methoxymethoxy) silane, ethyltri (methoxymethoxy) sila , Vinyltri (methoxymethoxy) silane, phenyltri (methoxymethoxy) silane, methyltri (ethoxymethoxy) silane, ethyltri (ethoxymethoxy) silane, vinyltri (ethoxymethoxy) silane, phenyltri (ethoxymethoxy) silane, tetra (methoxymethoxy) Alkoxyalkoxysilanes such as silane and tetra (ethoxymethoxy) silane; Aminoxysilanes such as methyltris (N, N-diethylaminoxy) silane; Methyltris (N-methylacetamido) silane, Methyltris (N-butylacetamido) silane, Methyltris ( N-cyclohexylacetamido) silane and other amide silanes; methyl triisopropenoxy silane, vinyl triisopropenoxy silane, phenyl triisopropenoxy sila Alkenoxy silanes and the like; Methyltriacetoxysilane include acetoxy silane and vinyl triacetoxy silane.

  Examples of siloxane include partial hydrolysis-condensation products of the above silane compounds. The weight average molecular weight of the siloxane is not particularly limited, but is preferably an oligomer obtained by polymerizing 2 to 100, preferably 2 to 20, silane compounds. The siloxane may be a mixture of oligomers having a plurality of degrees of polymerization.

上記式（３）中、Ｒ^３は、互いに独立に、炭素原子数１〜１０のアルキル基、又は炭素原子数２〜１０のアルコキシアルキル基であり、Ｗは炭素原子数１〜２０、好ましくは１〜１０の、非置換又は置換の二価炭化水素基である。Ｗで示される二価炭化水素基は、直鎖状であっても分岐構造を有していてもよいが、特にはメチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基等の直鎖アルキレン基が好ましい。中でも、特にエチレン基が好ましい。 Moreover, as said (B) component, the silane compound shown by following General formula (3) may be sufficient.

In the above formula (3), R ³ is independently an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, and W is 1 to 20 carbon atoms, preferably 1 to 10 unsubstituted or substituted divalent hydrocarbon groups. The divalent hydrocarbon group represented by W may be linear or have a branched structure, but in particular, linear alkylene such as methylene group, ethylene group, propylene group, butylene group and hexylene group. Groups are preferred. Among these, an ethylene group is particularly preferable.

  The component (B) may be used alone or in combination of two or more. Moreover, you may use together the silane compound and / or siloxane which have two hydrolyzable groups in 1 molecule in the range which does not prevent the effect of this invention.

  (B) The quantity of a component is 0.1-40 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-20 mass parts. When the amount of the component (B) is less than the lower limit value, there is a risk that curability and storage stability are reduced. Moreover, when the said upper limit is exceeded, there exists a possibility that not only it may become disadvantageous in price, but the elongation of hardened | cured material may fall or the deterioration of durability may be caused. In particular, when the component (A) contains a diorganopolysiloxane having a hydroxyl group at the terminal, such an amount that the number of hydrolyzable groups in the component (B) exceeds the number of hydroxyl groups in the component (A). It is preferable that

[Component (C)]
Component (C) is a carboxylic acid titanium salt. This component is a curing catalyst and functions to impart fast curability to the composition. The carboxylic acid is preferably a monovalent carboxylic acid having a saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms. More preferably, a monovalent carboxylic acid having a saturated hydrocarbon group having 6 to 18 carbon atoms or a monovalent carboxylic acid having an unsaturated hydrocarbon group having 6 to 21 carbon atoms is preferable. Examples include octylic acid, naphthenic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecane, octadecanoic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and the like. In particular, octylic acid or naphthenic acid titanium salt is preferred. The titanium salt of carboxylic acid may be used alone or in combination of two or more. Moreover, the titanium salt which has multiple types of carboxylic acid may be sufficient.

  (C) The quantity of a component is 0.001-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-5 mass parts. And most preferably 0.2-2 parts by mass. When the amount of component (C) is less than the above lower limit, desired rapid curability cannot be obtained. On the other hand, if the amount of component (C) exceeds the above upper limit, the curing reaction of the composition is too fast, which may lead to a decrease in pot life, a decrease in elongation of the cured product, or a deterioration in durability.

[(D) component]
Component (D) is a carboxylic acid. The present invention is characterized in that the carboxylic acid and the titanium salt of the above (C) carboxylic acid are combined, thereby suppressing the gelation of the composition after mixing each component, and reducing the pot life. It is possible to ensure sufficient workability by increasing the length. The carboxylic acid is preferably a monovalent carboxylic acid having a saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms. More preferably, a monovalent carboxylic acid having a saturated hydrocarbon group having 6 to 18 carbon atoms or a monovalent carboxylic acid having an unsaturated hydrocarbon group having 6 to 21 carbon atoms is preferable. Examples include octylic acid, naphthenic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecane, octadecanoic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and the like. In particular, octylic acid or naphthenic acid is preferable. These may be used alone or in combination of two or more.

  (D) The quantity of a component is 0.001-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.005-5 mass parts, More preferably, it is 0.02-2 mass parts. When the amount of the component (D) is less than the above lower limit, the effect of suppressing the gelation of the composition and the effect of extending the pot life cannot be obtained. Moreover, when the amount of the component (D) exceeds the above upper limit, the durability of the composition may deteriorate, or the adhesiveness may deteriorate. In particular, the amount of the component (D) is 0.1% to 500%, preferably 0.5% to 300%, more preferably 1% to 150% with respect to the mass part of the component (C).

[(E) component]
The organopolysiloxane composition of the present invention may further contain a silane compound and / or siloxane having at least one epoxy group in the molecule in order to impart adhesiveness to the cured product. In the organopolysiloxane composition of the present invention, it is preferable not to use a silane compound containing a primary or secondary amino group which is usually used as an adhesion-imparting agent.

  Epoxy group-containing silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Examples include trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Examples of the epoxy group-containing siloxane include a partial hydrolysis condensate of the epoxy group-containing silane compound and a partial hydrolysis condensate of the epoxy group-containing silane compound and various silane compounds. Examples of various silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, Examples thereof include diphenyldimethoxysilane and phenyltriethoxysilane. The silane compound and siloxane may be used alone or in combination of two or more.

  (E) The quantity of a component is 0.05-20 mass parts with respect to 100 mass parts of (A) component, It is preferable that it is 0.1-10 mass parts especially. When the amount of the component (E) is too large, the durability and curability of the composition may be deteriorated, and when it is too small, the effect of improving the adhesiveness may not be obtained.

[(F) component]
The organopolysiloxane composition of the present invention can further contain calcium carbonate. By containing calcium carbonate, the sagging prevention property of the composition of this invention can be improved, and workability | operativity can further be improved. Moreover, a favorable mechanical characteristic can also be provided to the hardened | cured material of this composition. As calcium carbonate, heavy (or pulverization method) calcium carbonate, colloidal (or precipitation method) calcium carbonate, surface of these calcium carbonates with organic acids such as fatty acids and resin acids, organic acid alkali metal salts, organic acid esters, etc. Treated powder can be used. The average particle diameter of calcium carbonate is not particularly limited, but the average particle diameter of heavy calcium carbonate is preferably 0.5 to 10 μm, particularly preferably 1.0 to 3.2 μm. The average particle diameter is a value calculated from a specific surface area calculated by measuring by an air permeation method. In addition, colloidal calcium carbonate has an average primary particle size measured by an electron microscope of preferably 0.01 to 0.5 μm, particularly preferably 0.03 to 0.1 μm. A commercial item can be used for calcium carbonate.

  The amount of the component (F) is preferably 1 to 400 parts by mass, more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the component (A). (F) When the quantity of a component exists in the said range, the handling workability | operativity of a composition becomes favorable.

[Other ingredients]
In addition, the organopolysiloxane composition of the present invention can further contain generally known additives in addition to the components (A) to (F) as long as the effects of the present invention are not impaired. Additives include dry silica, wet silica, quartz fine powder, diatomaceous earth powder, aluminum hydroxide powder, particulate alumina, magnesia powder, zinc oxide powder, and silanes, silazanes, low polymerization degree poly Fine powdery inorganic fillers surface-treated with siloxanes, pigments, dyes, colorants such as fluorescent brighteners, antibacterial agents, fungicides, plasticizers and the like.

  In the organopolysiloxane composition of the present invention, at least the component (A), the component (B) and the component (E) are stored in separate packages from the viewpoint of storage stability and the like, and these are mixed in use. A multi-component organopolysiloxane composition is preferred. The component (C), the component (D), and the component (F) can be mixed and stored in the component (A), the component (B), or both. In particular, the component (A) is preferably packaged separately from the component (C) and the component (D), thereby improving the storage stability of the composition. The component (F) is particularly preferably packaged separately from the component (B) and the component (E), thereby improving the storage stability of the composition.

  The organopolysiloxane composition of the present invention can be prepared by uniformly mixing the above components. For example, the (A) component, and if necessary, the (F) component and other components are uniformly mixed to form the first agent. On the other hand, (B) component, (C) component, (D) component, and (E) and other components are mixed uniformly as needed to make a second agent. The mixing may be performed using a known mixer such as a three-roll, planetary mixer, or universal mixer. The first agent and the second agent are weighed in a predetermined amount before use and mixed by stirring with a metal spatula or the like, or mixed with a static mixer, dynamic mixer, or the like to prepare the organopolysiloxane composition of the present invention. be able to. The mixing ratio of the first agent and the second agent may be appropriately adjusted according to the amount of each component described above, but preferably, the second agent is 0.5 to 200 parts by mass with respect to 100 parts by mass of the first agent. In particular, it is preferable to mix at a ratio of 1 to 120 parts by mass, and more particularly 1.5 to 100 parts by mass.

The organopolysiloxane composition of the present invention has a pot life of 30 minutes or more at room temperature, particularly 1 hour or more, more particularly 1 to 24 hours, more particularly 2 to 24 hours, and a long pot life. It is characterized by that. In the present invention, the pot life at room temperature is the time during which the composition can be used in an environment of a temperature of 23 ° C. ± 5 ° C. and a humidity of 50% RH ± 5%. The usable time is a time during which the composition packed in the cartridge can be easily discharged. More specifically, the pot life in the present invention means that the composition packed in the cartridge does not gel in an environment of a temperature of 23 ° C. ± 5 ° C. and a humidity of 50% RH ± 5%. This is the time during which 2 g or more can be discharged per second when the composition is discharged from the cartridge by applying a pressure of ² kgf / cm ² using a nozzle having an inner diameter of 5 mm at the tip.

  Heating and cooling are not required to cure the organopolysiloxane composition of the present invention. The organopolysiloxane composition of the present invention can be cured by allowing it to stand for about 1 day to 1 week at about room temperature, for example, 5 to 40 ° C.

  As described above, the organopolysiloxane composition of the present invention has good workability because it has a long pot life. Moreover, it can have the long pot life equivalent to or more than the composition using a tin compound. Further, the composition is excellent in surface curability, thin film curability, internal curability, and storage stability, and the resulting cured product does not cause coloring or discoloration. Therefore, the organopolysiloxane composition of the present invention is useful as a sealing material, an adhesive, a coating agent, or a potting agent. The method of using the organopolysiloxane composition of the present invention as a sealing material, an adhesive, a coating agent, or a potting agent may be a conventionally known method. Examples of the target articles include architectural structures, civil engineering structures, electric / electronic parts, automobile parts, electric wires / cables, and the like. In particular, it can be suitably used as a sealing material for a building structure or a civil engineering structure, for example, an elastic sealing material for construction, a highly durable sealing material for construction, a sealing material for glazing, and a curtain wall. It is useful as a sealing material, a sealing material for multi-layer glass, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. In addition, all the parts in an Example mean a mass part. The viscosity is a value measured by a rotational viscometer.

[Example 1]
Polydimethylsiloxane 60 parts (viscosity 50,000 mPa · s, manufactured by Shin-Etsu Chemical Co., Ltd.) each having one hydroxyl group bonded to a silicon atom at both ends, colloidal calcium carbonate powder (Carlex 300, primary particle size (electron Microscope): 0.05 μm, surface treatment agent: fatty acid, manufactured by Maruo Calcium Co., Ltd.) 40 parts were uniformly mixed using a universal mixer and three rolls to prepare the first agent. On the other hand, 1 part of decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 part of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and titanium octylate (manufactured by Alfa Aesar) 1 part and 1 part of octylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were uniformly mixed using a universal mixer to prepare a second agent. An organopolysiloxane composition was prepared by mixing with 100 parts of the first agent at a ratio of 3.5 parts of the second agent.

[Example 2]
A first agent was prepared with the same composition as in Example 1. On the other hand, a second agent was prepared with the same composition as in Example 1 except that the amount of octylic acid was 0.1 part. An organopolysiloxane composition was prepared by mixing 2.6 parts of the second agent with 100 parts of the first agent.

[Example 3]
A first agent was prepared with the same composition as in Example 1. On the other hand, 1 part of methyltrimethoxysilane partially hydrolyzed condensate (a mixture of oligomers having a polymerization degree of 2-8, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 part of 3-glycidoxypropyltrimethoxysilane, and octyl A second agent was prepared by uniformly mixing 0.7 parts of titanium acid and 0.2 parts of octylic acid using a universal mixer. An organopolysiloxane composition was prepared by mixing 2.4 parts of the second agent with respect to 100 parts of the first agent.

[Comparative Example 1]
A first agent was prepared with the same composition as in Example 1. On the other hand, a second agent was prepared with the same composition as Example 1 except that 1 part of octylic acid was not mixed. An organopolysiloxane composition was prepared by mixing 2.5 parts of the second agent with 100 parts of the first agent.

[Comparative Example 2]
A first agent was prepared with the same composition as in Example 1. On the other hand, a second agent was prepared with the same composition as in Example 1 except that 1 part of lactic acid was used instead of 1 part of octylic acid. An organopolysiloxane composition was prepared by mixing with 100 parts of the first agent at a ratio of 3.5 parts of the second agent.

[Comparative Example 3]
A first agent was prepared with the same composition as in Example 1. On the other hand, 1 part of decyltrimethoxysilane, 0.5 part of 3-glycidoxypropyltrimethoxysilane, 1 part of titanium tetra-n-butoxide (manufactured by Matsumoto Fine Chemical Co., Ltd.) and 1 part of octylic acid are universally mixed. The second agent was prepared by mixing uniformly using a machine. An organopolysiloxane composition was prepared by mixing with 100 parts of the first agent at a ratio of 3.5 parts of the second agent.

[Comparative Example 4]
A first agent was prepared with the same composition as in Example 1. On the other hand, a second agent was prepared with the same composition as Comparative Example 3 except that 1 part of octylic acid was not mixed. An organopolysiloxane composition was prepared by mixing 2.5 parts of the second agent with 100 parts of the first agent.

[Comparative Example 5]
A first agent was prepared with the same composition as in Example 1. On the other hand, 1 part of decyltrimethoxysilane, 0.5 part of 3-glycidoxypropyltrimethoxysilane, 1 part of titanium octylate and 1 part of octylic acid, 50% mineral spirit solution of iron (II) naphthenate A second agent was prepared by uniformly mixing 1 part of Kojunyaku Co., Ltd.) using a universal mixer. An organopolysiloxane composition was prepared by mixing 4.5 parts of the second agent with respect to 100 parts of the first agent.

[Comparative Example 6]
A first agent was prepared with the same composition as in Example 1. On the other hand, the same as Comparative Example 5 except that 1 part of iron (III) octylate 50% mineral spirit solution (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1 part of 50% mineral spirit solution of iron (II) naphthenate. A second agent was prepared with a composition. An organopolysiloxane composition was prepared by mixing 4.5 parts of the second agent with respect to 100 parts of the first agent.

[Comparative Example 7]
A first agent was prepared with the same composition as in Example 1. On the other hand, a base agent and a curing agent were prepared in the same manner as in Comparative Example 3 except that 1 part of naphthyrate iron (II) 50% mineral spirit solution was used instead of 1 part of octylic acid of Comparative Example 3, and 100 parts of the base agent was prepared. On the other hand, it was mixed at a ratio of 3.5 parts of the curing agent.

[Comparative Example 8]
A first agent was prepared with the same composition as in Example 1. On the other hand, a base agent and a curing agent were prepared in the same manner as in Comparative Example 3 except that 1 part of iron (III) octylate 50% mineral spirit solution was used instead of 1 part of octylic acid in Comparative Example 3, and 100 parts of the base agent was prepared. On the other hand, it was mixed at a ratio of 3.5 parts of the curing agent.

[Comparative Example 9]
A first agent was prepared with the same composition as in Example 1. On the other hand, a second agent was prepared with the same composition as in Example 1 except that 1 part of titanium octylate was 25 parts of titanium octylate and 1 part of octylic acid was 25 parts of octylic acid. An organopolysiloxane composition was prepared by mixing at a ratio of 51.5 parts of the second agent to 100 parts of the first agent.

[Reference Example 1]
A first agent was prepared with the same composition as in Example 1. On the other hand, 1 part of decyltrimethoxysilane, 0.5 part of 3-glycidoxypropyltrimethoxysilane and 0.05 part of dioctyltin dilaurate are uniformly mixed using a universal mixer to prepare a second agent. did. An organopolysiloxane composition was prepared by mixing at a ratio of 1.55 parts of the second agent with respect to 100 parts of the first agent.

  Table 1 shows the composition of each organopolysiloxane composition prepared in the above Examples and Comparative Examples.

[performance test]
About each composition obtained above, confirmation of the presence or absence of gelatinization, measurement of discharge amount, evaluation of pot life, evaluation of curability (surface curability, thin film curability, internal curability), and colorability Evaluation of discoloration, storage stability and durability was carried out by the following methods.

-Confirmation of the presence or absence of gelation Each said composition was packed in the resin cartridge with a nozzle. After leaving at 23 ° C. and 50% RH for 30 minutes, 1 hour and 2 hours, the composition is discharged using a cartridge gun, and the composition is confirmed to be gelled by spreading it into a sheet. did. After 30 minutes, 1 hour, and 2 hours, the case where no gel was formed was evaluated as good (◯), and the case where a gel was formed was evaluated as bad (×). The results are shown in Table 2.

-Measurement of discharge amount Each of the above compositions was packed in a resin cartridge with a nozzle. After leaving at 23 ° C. and 50% RH for 30 minutes, 1 hour and 2 hours, using a nozzle with an inner diameter of 5 mm at the tip, applying a pressure of ² kgf / cm ² for 5 seconds and extruding the composition for 5 seconds The weight of the object (discharge amount, g) was measured. The results are shown in Table 2. In addition, the measurement of the said discharge amount was not implemented about the composition evaluated as "bad" in the confirmation test of the said gelation presence / absence.

It is evaluated in the confirmation test of the presence or absence of Evaluation of gelation-pot life "good", and when the discharge amount of 5 seconds in the measurement of the ejection amount is more than 10 g, and it is possible to use the composition The time during which the usable state was judged and maintained was listed in Table 2 as the pot life. The case where the pot life was 1 hour or more was evaluated as good (◯), and the case where the pot life was less than 1 hour was evaluated as bad (×). The results are shown in Table 2.

-Each said composition was filled in the glass petri dish of surface hardening diameter 27mm and depth 14mm, and it left still at 23 degreeC and 50% RH for 24 hours. Then, the presence or absence of surface viscosity (tack) was confirmed. The case where there was no tack on the surface was evaluated as good (◯), and the case where there was tack on the surface was evaluated as bad (×). The results are shown in Table 2.

-Two metal plates having a thickness of 0.1 mm are arranged in parallel as spacers on a thin film curable glass plate, the above compositions are extruded between the metal plates, and the thickness is about 0 using another metal plate. After spreading to 1 mm, it was allowed to stand at 23 ° C. and 50% RH for 24 hours. Then, the presence or absence of the viscosity (tack) of the thin film surface was confirmed. The case where there was no tack on the surface was evaluated as good (◯), and the case where there was tack on the surface was evaluated as bad (×). The results are shown in Table 2.

-Each said composition was filled in the glass petri dish of internal hardening diameter 27mm and depth 14mm, and it left still at 23 degreeC and 50% RH for 24 hours. Thereafter, the cured product was removed from the petri dish, and the presence or absence of viscosity (tack) at the bottom was confirmed. The case where there was no tack at the bottom was evaluated as good (◯), and the case where there was tack at the bottom was evaluated as bad (×). The results are shown in Table 2.

-Colorability Each said composition was left still at 23 degreeC and 50% RH for 24 hours. Thereafter, the color of the composition and the color of the first agent (main agent) were measured with a spectrocolorimeter, and the color difference (ΔE, L ^* a ^* b ^* color system) was calculated. If the color difference was less than 10, the coloration was small and therefore evaluated as good (◯), and if the color difference was 10 or more, the coloration was large and evaluated as bad (x). The results are shown in Table 2.

-Color change property After leaving each said composition for 7 days at 23 degreeC and 50% RH, the color was measured (initial value). Thereafter, each composition was allowed to stand at 50 ° C. and 90% RH for 7 days, and then further allowed to stand at 23 ° C. and 50% RH for 24 hours. The color of each composition after standing was measured, and the color difference from the initial value was calculated. If the color difference is less than 10, the discoloration is small and thus evaluated as good (◯), and if the color difference is 10 or more, the discoloration is large and evaluated as bad (x). The results are shown in Table 2.

-Preservative 1st agent and 2nd agent were left still at 50 degreeC for 7 days, and it left still after that at room temperature for 24 hours. Then, the 1st agent and the 2nd agent were mixed and surface curability and internal curability were evaluated by the method as described above about the obtained composition. When both the surface curability and the internal curability were good, the storage stability was evaluated as good (◯). When mixing of the first agent and the second agent was impossible, or when evaluation of at least one of surface curability and internal curability was poor, it was evaluated that storage stability was poor (x). The results are shown in Table 2. In addition, about the composition evaluated that at least one of surface curability or internal curability was bad in the state before long-term storage, the said preservability was not implemented.

Durability Durability classification 9030 test described in JIS A 5758 was performed. Pass / fail was determined by the determination method described in JIS A 5758. The case of passing was evaluated as being good (◯), and the case of failing was evaluated as being poor (×). The results are shown in Table 2.

・ Comprehensive evaluation Overall evaluation is good when the presence / absence of gelation, pot life, surface curability, thin film curability, internal curability, colorability, discoloration, storability and durability are all good. (○) was evaluated, and a case where there was even one bad item was evaluated as a poor overall evaluation (×). The results are shown in Table 2.

  As shown in Table 2, a composition containing no carboxylic acid and containing only a titanium salt of carboxylic acid has a short pot life (Comparative Example 1). A composition containing lactic acid instead of carboxylic acid is inferior in surface curability, thin film curability, and internal curability (Comparative Example 2). A composition using a titanium alkoxide compound instead of a carboxylic acid titanium salt increases in viscosity or gels immediately after mixing, and has a very short pot life. Moreover, it is inferior to surface curability, thin film curability, and internal curability (Comparative Examples 3 and 4). A composition containing no carboxylic acid and containing a titanium alkoxide compound and an iron compound increases in viscosity or gels immediately after mixing, and has a very short pot life. Moreover, it is inferior to surface curability, thin film curability, and internal curability, and also produces coloring and discoloration (Comparative Examples 7 and 8). In contrast, the organopolysiloxane composition of the present invention has a long pot life, excellent surface curability, thin film curability, internal curability, and storage stability, and does not cause coloring or discoloration (Example 1). ~ 3). Moreover, the pot life of the organopolysiloxane composition of the present invention is longer than or equal to that of the composition using the tin compound (Reference Example 1). Therefore, according to the present invention, it is possible to provide an organopolysiloxane composition that can ensure a long pot life without using a tin compound and is excellent in curability.

  According to the present invention, it is possible to provide a multi-component room temperature curable organopolysiloxane composition that has a long pot life and good curability without using a tin compound. The composition is excellent in surface curability, thin film curability, internal curability, and storage stability, and does not cause coloring or discoloration. Therefore, the organopolysiloxane composition of the present invention is useful as a sealing material, an adhesive, a coating agent, a potting agent, and the like, and can be suitably used particularly as a sealing material for construction and civil engineering applications.

Claims (6)

(A) Diorganopolysiloxane having a hydroxyl group and / or a hydrolyzable group at both ends of the molecular chain and having a viscosity of 20 to 1,000,000 mPa · s at 25 ° C .: 100 parts by mass
10 to 100 parts by mass of 100 parts by mass of the component (A) is a diorganopolysiloxane having a hydroxysilyl group at both ends of the molecular chain.
(B) Silane compound and / or siloxane having 3 or more alkoxy groups bonded to silicon atoms in the molecule (provided that the component (B) is different from the component (A)): 0.1 to 40 parts by mass ,
(C) One type selected from a monovalent carboxylic acid titanium salt having a saturated hydrocarbon group having 6 to 18 carbon atoms and a monovalent carboxylic acid titanium salt having an unsaturated hydrocarbon group having 6 to 21 carbon atoms Or 2 or more types : 0.001 to 20 parts by mass, and (D) 1 having a monovalent carboxylic acid having a saturated hydrocarbon group having 6 to 18 carbon atoms and an unsaturated hydrocarbon group having 6 to 21 carbon atoms One or more selected from divalent carboxylic acids: The organopolysiloxane composition containing 0.001 to 20 parts by mass and containing no iron compound .   The organopolysiloxane composition according to claim 1, which has a pot life of 1 hour or more at room temperature. Additionally, (E) having at least one epoxy group in the molecule, comprising a silane compound and / or a siloxane claim 1 or 2 organopolysiloxane composition. An article having a cured product of the organopolysiloxane composition according to any one of claims 1 to 3 . A building structure or a civil engineering structure having a cured product of the organopolysiloxane composition according to any one of claims 1 to 3 . A method of using the organopolysiloxane composition according to any one of claims 1 to 3 as one selected from a sealing material, a potting agent, a coating agent, and an adhesive.