TWI389979B - Room temperature hardened organopolysiloxane composition - Google Patents

Description

Room temperature hardening organopolyoxane composition

The present invention relates to a room temperature hardening property which is suitable for a polyfluorene-based sealant, an adhesive, a coating agent or a heat-hardening agent, in order to ensure an extremely long working time and to hardly volatilize a reactive decane compound when not hardened. Organic polyoxane composition.

Condensation-curable polyfluorene-based sealants, adhesives, coating agents, and bottling compositions are used in many fields such as construction, electrical and electronic, conveyors, electrical parts, and home appliances. In general, a condensation-hardening polysulfonated sealant, an adhesive, a coating agent, and a heat hardener composition for use in such a use are those having at least three hydrolyzable groups bonded to a ruthenium atom in one molecule. A decane compound which is a crosslinking agent and/or a partial hydrolyzate thereof. Specific examples are, for example, alkyltrimethoxydecane, alkyltributoxydecane, alkyltriethoxydecyloxytriisopropoxydecane, or a partial hydrolyzate thereof. These reactive decanes are extremely reactive and are therefore suitable for most of the rapid cure properties of the above applications. However, for the roofing waterproofing, roof coating waterproofing, underwater structural coatings, ship bottom coatings, wall coatings, etc., coating, sealing, adhesion, coating, heat hardening, adhesion object position integration, surface correction When it is equal, it takes a very long time to work, and the cross-linking agent generally used is extremely difficult to work as long as the above-mentioned operator.

Moreover, the decane single component component derived from the crosslinking agent, the heating shape change after curing of the low molecular weight siloxane oligomer, the organic coating uncoordinated, the electrical contact short circuit, the conduction failure, and the working place Landslides and other discomforts appear. In the prior art, the main reason is to make a low molecular cyclic polyoxane contained in a base polymer. However, the removal of the uppermost limit of the low molecular cyclic polyfluorene from the base polymer is still largely unable to solve the problem completely, and the volatile decane single component derived from the crosslinker is also responsible for this.

The condensing-curing type of the fluorinated sulphur-sealing material which can be used for a long period of time is disclosed in JP-A-51-62850, JP-A-52-108796, JP-A-55-92761 (Patent Documents 1 to 3) ) a deaminated oxy-type composition. However, the de-aminooxy-type composition produces a characteristic odor with a dialkylhydroxylamine upon hardening, and a good cured product is obtained while extending the usable time by about 12 hours to 24 hours. Further, a method of adding a volatile organic oxirane, such as a volatile organic polysiloxane, is produced by a method of adding a volatile organic oxirane, such as Patent No. 2,972,231, and JP-A-2001-181508 (Patent Documents 4 and 5). Volume shrinkage around the surrounding and hardened. The deodorant-type composition is replaced by a low-odor composition, such as a dealcoholic composition. For example, Japanese Patent Publication No. Sho 39-27643 (Patent Document 6) discloses a composition comprising a hydroxyl terminated molecular organopolyoxane and an alkoxydecane and an organotitanium compound. .

Further, JP-A-55-43119 (Patent Document 7) discloses a composition comprising an alkoxy fluorenylalkyl end-blocking organopolyoxane, an alkoxy decane, and a titanium alkoxide. Further, Japanese Patent Publication No. Hei 7-39547 (Patent Document 8) discloses an alkoxyalkyl group-terminated chain polyorganosiloxane containing a decanevinyl group, alkoxy decane and a titanium alkoxide. Composition. Further, the alkoxy fluorenyl group-terminated chain polyorganosiloxane and the hydroxy terminal organopolyoxane, alkoxy decane, and titanium are contained in JP-A-62-207369 (Patent Document 9). The composition is used to improve oil swellability and Shelf life. Various production methods are discussed for these dealcoholized compositions, and the stability of various properties such as stability (inhibition of change over time) and oil swellability are preserved, and in particular, the preservation stability surface characteristic of the dealcoholized composition is A so-called one-liquid composition that emphasizes deep hardening without stability in the absence of moisture. In contrast, there is almost no detailed discussion about a two-liquid type composition having deep hardenability as a one-liquid type.

As a two-liquid type of dealcoholized KTV composition, an organic polysiloxane or a trialkoxy group which is blocked by a sterol group at both ends is disclosed in Patent No. 2,784,045 (Patent Document 10). A composition of decane and its partial hydrolyzate, calcium carbonate, and organometallic catalyst. Further, Patent Publication No. 3210424 (Patent Document 11) discloses an organopolyoxane which is blocked by a sterol group at both ends, a trioxane having two alkoxy groups, a tris or a tetraalkoxy group. a mixture of decane and a partial hydrolyzate or a hardening catalyst, but using alkoxy decane as a crosslinking agent, in order to ensure sufficient usable time, the amount of catalyst is reduced, and thus it is impossible to obtain Sufficient mechanical properties.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. H--------- [Patent Document 5] Japanese Patent Publication No. JP-A-H07-43-119 [Patent Document 9] JP-A-62-207369 (Patent Document 10) Patent No. 2,784,045

The present invention has been made in view of the above problems, and is also applicable to a two-liquid type RTV which can easily ensure an extremely long working time without causing discomfort by volatilization of a decane monomer component derived from a volatile crosslinking agent. A room temperature curable organopolyoxane composition obtained from a cured rubber having a good rubber elasticity is an object thereof.

In order to achieve the above object, the inventors of the present invention have found that the (A) molecular chain has a hydroxyl group-terminated diorganopolysiloxane: 100 parts by mass, and (B) has a molecular oxygen chain end. Hydrolyzable alkylene group of diorganopolyoxyalkylene oxide: 1 to 200 parts by mass, (C) tin catalyst: 0.01 to 10 parts by mass of room temperature curable organopolyoxane composition for easy securing The long working time is not caused by the volatilization of the volatile component of the decane monomer, but also the hardened rubber with good rubber elasticity. It is suitable for sealant, adhesive, coating agent and heating hardener. ,Wait. That is, after the alkoxy decane and a partial hydrolyzate thereof are used as a crosslinking agent, the polymer alkoxy siloxane having a low autoreactivity can be substituted for a sufficient usable time and hardening. The present invention is further completed by a room temperature curable organopolyoxane composition of mechanical properties.

That is, the present invention provides a diorganopolyoxane (R) having the characteristics of (A) a diorganopolyoxyalkylene group (B) having a hydroxyl group blocked at both ends of the molecular chain (B) ¹ O) _m R ² _{3 - m} Si-O-(R ² ₂ SiO) _k -SiR ² _{3 - m} (OR ¹ ) _m (wherein R ¹ is the same or different carbon number of 1 to 6 a group or alkoxyalkyl group having 2 to 10 carbon atoms, R ² being the same or different unsubstituted or substituted monovalent hydroxyl group, m being an integer of 1 to 3, and k being an integer of 10 or more) 1 to 100 mass (C) tin catalyst 0.01 to 10 parts by mass of a room temperature curable organopolyoxane composition.

The room temperature curable organopolyoxane composition of the present invention can easily ensure extremely long working time. Further, since the composition hardly volatilizes the reactive decane compound at the time of final hardening, it is possible to control the occurrence of discomfort such as uncoordinated organic coating and short circuit of electrical contact. Moreover, the composition has good hardness. Therefore, the composition is suitable for use in a polyfluorene-based sealant, an adhesive, a coating agent, and a heat-curing agent in applications where extremely long working time is required.

[Best form of implementation of the invention]

Hereinafter, the present invention will be described in more detail.

[(A) ingredients]

(A) A diorganopolyoxyalkylene group in which both ends of the molecular chain of the component are linked by a hydroxyl group, which is represented, for example, by the following general formula (1).

HO[Si(R) ₂ O] _n H (1)

In the general formula (1), R independently represents an unsubstituted or substituted monovalent hydrocarbon group. For this R, such as: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and some or all of hydrogen atoms of such hydrocarbon groups. A base that is replaced by a halogen atom such as fluorine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclohexyl group. Examples of the alkenyl group include a vinyl group and an allyl group. As the aryl group, for example, a phenyl group or the like. As the halogen atom-substituted base such as: 3,3,3-trifluoropropyl and the like. Among these, a methyl group, a vinyl group, and a phenyl group are particularly preferable, and a methyl group is more preferable.

In the general formula (1), n is an integer of 10 or more, and the viscosity of the two organopolyoxane at 25 ° C is 10 to 1,000,000 mpa. s should be suitable, preferably 100~100,000 mpa. s, especially 300~50,000 mpa. The number of s is the best.

When the viscosity is too small, the mechanical properties of the hardened material (rubber) are not obtained. On the other hand, if the viscosity is too large, the viscosity of the composition becomes large, and the workability is lowered. The viscosity is measured by a rotary viscometer.

(A) Specific ingredients such as: (In the formula, A is a methyl group or a phenyl group, n is the same as described above, and n1, n2 and n3 are examples in which n1+n2=n and n1+n3=n are 1 or more integers).

[(B) ingredients]

The polyoxane which is the component (B) is a polyoxane represented by the following formula. (R ¹ O) _m R ² _{3 - m} Si-O-(R ² ₂ SiO) _k -SiR ² _{3 - m} (OR ¹ ) _m (wherein R ¹ is the same or different carbon number 1 to 6 An alkyl group or an alkoxyalkyl group having 2 to 10 carbon atoms, and R ² is an unsubstituted or substituted monovalent hydrocarbon group which is the same or different, m is an integer of 1 to 3, and k is an integer of 10 or more).

In the above formula, R ¹ is the same or different alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, and is an alkyl group such as methyl, ethyl or propyl. Examples of cyclohexyl groups, such as methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl, hexyloxy , heptoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypropyl, Ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxy Examples of a hexyl group, a methoxyheptyl group and the like.

Among them, a methyl group or an ethyl group is preferred.

Further, R ² is an unsubstituted or substituted monovalent hydrocarbon group of the same or different, a carbon number of 1 to 20, particularly an alkyl group of 1 to 6, a carbon number of 6 to 20, particularly an aryl group of 6 to 12, or Examples of such a portion in which a hydrogen atom is replaced by a halogen atom. Specifically, as an alkyl group, such as methyl, ethyl, propyl, cyclohexyl, etc., as an alkenyl group such as: vinyl, allyl, etc., as an aryl group such as: benzene Examples of the radical or halogen-substituted substituents such as 3,3,3-trifluoropropyl and the like.

Among them, methyl, vinyl, phenyl, 3,3,3-trifluoropropyl is preferred, and methyl is particularly preferred.

m is an integer from 1 to 3, preferably 2 and 3.

k is an integer of 10 or more, and the (B) component has a viscosity of 10 to 1,000,000 mpa at 25 ° C. The range of s, especially 100~500,000 mpa. The range of s is good. When the viscosity is too small, the mechanical properties of the cured product (rubber) cannot be fully obtained. Conversely, if the viscosity is too large, the viscosity of the composition becomes high, and the workability is lowered. Among them, the viscosity is a value measured by a rotary viscometer.

(B) The component of the organic polyoxane may be used in combination with two or more different substituents, viscosity (value of k), value of m, and the like.

The crosslinking agent is a condensation reaction of alkane having an alkoxy group in a oxoxane having a hydroxyl group at both ends, or a decane having a hydrogenated decyl group and an alkoxy group in a oxane having a hydroxyl group at both terminals. The condensation reaction can be easily carried out in the presence of a catalyst.

The compounding amount of the (B) component diorganopolysiloxane is 1 to 200 parts by mass, preferably 10 to 150 parts by mass, per 100 parts by mass of the (II) component organopolyoxane. When it is less than 1 part by mass, sufficient hardenability cannot be obtained, and if it exceeds 200 parts by mass, the hardenability of the deep portion of the composition is lowered, and workability is also lowered.

[(C) ingredients]

The tin catalyst of the component (C) is used as a catalyst for the condensation reaction of the component (A) with the component (B) in the composition of the present invention. The tin-based catalyst capable of promoting the condensation reaction between the component (A) and the component (B) is not particularly limited, and a tin ester compound such as dioctanoate tin or dibutyltin diacetate may be generally used. Dibutyltin dilaurate, dibutyltin dioctanoate, isoalkyltin ester compound. These may be used alone or in combination of two or more.

Titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis(2-ethylhexyloxy), dipropoxy group, which is known as a hardening catalyst for a room temperature curable organopolyfluorene composition. A titanate or a titanium chelate compound such as bis(ethylmercaptoacetone)titanium or titanium isopropoxyoctanediol cannot achieve a sufficient use time.

The compounding amount of the component (C) is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the (A) component diorganopolysiloxane. When it is less than 0.01 parts by mass, sufficient hardening characteristics cannot be obtained, and if it exceeds 10 parts by mass, the durability of the composition is lowered.

[(D) ingredients]

The filler of the component (D) is arbitrarily used as a reinforcing agent and a bulking agent in the composition of the present invention. Examples of fillers of the component (D) include: fuming cerium oxide, wet cerium oxide, precipitated cerium oxide, calcium carbonate and other reinforcing fillers, metal oxides such as alumina and zinc oxide, and metals. Examples of hydroxides, carbon black, glass particles, glass spheres, resin pellets, and resin spheres. Ideally, it is aerosolized cerium oxide, precipitated cerium oxide, and calcium carbonate. These fillers may not be subjected to surface treatment, and may be subjected to surface treatment by a known treating agent.

When the filler of the component (D) is blended in the composition of the present invention, the amount of the filler of the component (A) is preferably from 1 to 500 parts by mass, particularly from 5 to 250 parts by mass, based on 100 parts by mass of the organopolysiloxane of the component (A). good. When the amount is less than 1 part by mass, the effect of addition is insufficient, and if it exceeds 500 parts by mass, the discharge property and workability of the composition of the present invention are lowered.

When the adhesiveness is required in the composition of the present invention, it is preferred to use the (E) decane coupling agent as the adhesion-imparting component. As a decane coupling agent, a known one can be used. Particularly suitable as a hydrolyzable group such as: alkoxyalkyl, alkoxy alkoxypropyltrimethoxydecane, β-(3,4-ethoxycyclohexyl)ethyltrimethoxynonane, ring Oxypropoxypropyltrimethoxydecane, glycidoxypropylmethyldiethoxydecane, N-β-(Aminoethyl)γ-Aminopropyltrimethoxydecane, Aminopropyltriethyl Examples of oxydecane, mercaptopropyltrimethoxydecane, glycidoxypropyltriisopropoxydecane, glycidoxypropylmethyldiisopropoxydecane, and the like. Among these, an amine decane coupling agent is particularly preferred.

The compounding amount of the decane coupling agent is preferably 0.1 to 20 parts by mass, particularly preferably 0.2 to 10 parts by mass, per 100 parts by mass of the diorganopolysiloxane of the component (A). If it is less than 0.1 part by mass, sufficient adhesion cannot be obtained. Conversely, if it exceeds 20 parts by mass, it is unfavorable.

[Other ingredients]

In addition to the above components, the composition of the present invention may be added with a known additive as an additive of a room temperature curable organopolyoxane composition. Such as: a polyether as a thixotropic enhancer, a non-reactive dimethylpolyphthalide oil as a plasticizer, an isoparaffin, a trimethylsulfoxane unit and a SiO ₂ unit as a crosslinking density enhancer. Examples of the networked polyoxane formed.

If necessary, it is also possible to add coloring agents such as pigments, dyes, and fluorescent whitening agents, antifungal agents, antibacterial agents, barrier agents, marine active agents, and other physiologically active additives, and non-reactive phenyl polycondensation of exuded oil. Surface modifying agents such as helium oxide oil, fluorine polyoxygenated oil, polyfluorene oxide and non-miscible organic liquid, toluene, xylene, solvent volatile oil, cyclohexane, methylcyclohexane, low boiling isoparaffin and the like.

[Modulation of composition. hardening]

The room temperature curable organopolysiloxane composition of the present invention is obtained by uniformly mixing the components (A) to (C) and, if necessary, the component (D), by a known rubber kneader such as a planetary mixer.

The composition of the present invention may also be mixed with (A), (B), (C), and if necessary (D) to be used in a one-liquid type, or separately as a component (B) and (C), when in use. Mixing two liquid types, such as: (A), (B), (D) components and (A), (C), (D) components of the two liquid type, (A), (B), (D) Two-component types such as ingredients and (C) can also be used. By making the two-liquid type, it ensures a more stable preservation.

The composition of the present invention can be applied to a predetermined substrate according to its application, and can be hardened at room temperature (generally 5 to 40 ° C, humidity 10 to 90 RH). At this time, it can be operated for a long time at room temperature.

[Use of composition]

The room temperature curable organopolyoxane composition of the present invention can be suitably used for a sealant, an adhesive, a coating agent, and a heat hardener.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following example, the viscosity is a value of 25 ° C as measured by a rotary viscometer.

[Example 1]

100 parts by mass of both ends with a hydroxyl group sealing viscosity of 700 mpa. s dimethyl polyoxane, 25 parts by mass of both ends via a decane bond with a trimethoxy decyl group with a viscosity of 900 mpa. To the dimethyl sulfoxide of s, 0.2 part by mass of tin dioctanoate was added and mixed until homogeneous, and the composition 1 was prepared.

[Comparative Example 1]

The composition 2 was prepared in the same manner as in Example 1 except that 0.2 part by mass of tin dioctanoate was replaced by 0.2 part by mass of tetrapropoxytitanium.

[Comparative Example 2]

5 parts by mass of methyltrimethoxydecane was substituted for 25 parts by mass of both ends via a decane bond with a trimethoxy decyl group with a viscosity of 900 mpa. The composition 3 was prepared in the same manner as in Example 1 except for dimethyl dimethyl siloxane.

The compositions of the examples and the comparative examples were placed in a glass culture dish, and the hardening property was confirmed by visual inspection and hand touch under the environment of 23±2° C. and humidity of 50±5% RH, and more than one day after hardening. After heating to 150 ° C, the shape change was visually determined. The results are shown in Table 1.

[Embodiment 2]

35 parts by mass of both ends with a hydroxyl group sealing viscosity of 50,000 mpa. s dimethyl polysiloxane, 40 parts by mass of colloidal carbonate, 25 parts by mass of both ends with a trimethyl decyloxy group with a viscosity of 100 mpa. s dimethyl polysiloxane, 10 parts by mass of both ends via a decane bond with a trimethoxy decyl group with a viscosity of 900 mpa. The composition 4 was prepared by adding 0.2 part by mass of tin dioctanoate to s dimethylpolyoxane and mixing until uniform.

[Example 3]

In the second embodiment, the composition 5 was prepared in the same manner as in Example 2 except that 0.2 part by mass of dioctyloctanoate was replaced by 1 part by mass of dioctyltin dilaurate.

[Comparative Example 3]

In Example 2, 5 parts by mass of methyltrimethoxydecane was substituted for 10 parts by mass of both ends via a decane bond to a trimethoxydecyl group with a viscosity of 900 mpa. The composition 6 was prepared in the same manner as in Example 2 except for dimethyl dimethyl siloxane.

The compositions of the examples and the comparative examples were placed in a glass petri dish, and the hardening property was determined by visual inspection and hand touch under the environment of 23±2° C. and humidity of 50±5% RH. After hardening for 1 day, the mixture was heated to After 150 ° C, the shape retention was determined. Further, a sheet having a thickness of 2 mm was produced, and after hardening for 7 days in an environment of 23 ° C ± 2 ° C and a humidity of 50 ± 5% RH, the rubber physical properties were measured in accordance with JIS-K-6249. The results are shown in Table 2.

[Example 4]

35 parts by mass of both ends with a hydroxyl group sealing viscosity of 50,000mpa. s dimethyl polysiloxane, 40 parts by mass of colloidal calcium carbonate, 25 parts by mass of both ends with a trimethyl decyloxy group with a viscosity of 100 mpa. s dimethyl polysiloxane, 10 parts by mass of both ends via a decane bond with a trimethoxy decyl group with a viscosity of 900 mpa. The composition 7 was prepared by adding 0.05 parts by mass of dioctyltin dilaurate and 0.2 part by mass of γ-aminopropylmethyldiethoxydecane to dimethyl methoxide.

[Example 5]

35 parts by mass of both ends with a hydroxyl group sealing viscosity of 50,000 mpa. s dimethyl polysiloxane, 40 parts by mass of colloidal calcium carbonate, 25 parts by mass of both ends with a trimethyl decyloxy group with a viscosity of 100 mpa. s dimethyl polysiloxane, 10 parts by mass of both ends via a decane bond with a trimethoxy decyl group with a viscosity of 900 mpa. 0.02 parts by mass of dioctyltin dilaurate and 0.2 parts by mass of γ-aminopropylmethyldimethoxydecane are added to s dimethyl polyoxane, and the mixture is mixed until homogeneous to prepare a composition. 8.

The composition of these examples was placed in a glass petri dish, and the hardening property was determined by visual inspection and hand touch under the environment of 23±2° C. and humidity of 50±5% RH. After hardening for 1 day, the temperature was heated to 150° C. To determine its shape retention. Further, a sheet having a thickness of 2 mm was produced, and after hardening for 7 days in an environment of 23 ± 2 ° C and a humidity of 50 ± 5% RH, the rubber physical properties were measured in accordance with JIS-K-6249. At the same time, the composition was applied to a floating glass plate at 23±2° C. and humidity of 50±5% RH, and after hardening for 7 days, the adhesion was determined by visual inspection and hand touch. The results are shown in Table 3.

Claims (4)

A two-component room temperature curable organopolyoxane composition characterized by comprising the first liquid of the following (A) and (B) below, and the following (C) is an essential component and may also be (A) a second liquid containing the following (A); (A) a di-organopolyoxyalkylene group having a hydroxyl group-terminated chain at both ends of the molecular chain represented by the general formula (1), 100 parts by mass of HO[Si(R) ₂ O _n H (1) (wherein R independently represents an unsubstituted or substituted monovalent hydrocarbon group, n is an integer of 10 or more), and (B) 1 to 100 parts by mass of the diorganopolyoxyalkylene represented by the following formula (R ¹ O) _m R ² _3-m Si-O-(R ² ₂ SiO) _k -SiR ² _3-m (OR ¹ ) _m (wherein R ¹ is the same or different carbon number 1 to 6 An alkyl group or an alkoxyalkyl group having 2 to 10 carbon atoms, and R ² is an unsubstituted or substituted monovalent hydrocarbon group which is the same or different, m is an integer of 1 to 3, and k is an integer of 10 or more), C) Tin catalyst is 0.01 to 10 parts by mass. The liquid-type room temperature curable organopolyoxane composition according to the first aspect of the patent application, wherein the (D) filler is further contained in an amount of from 1 to 500 parts by mass. A liquid-type room temperature curable organopolyoxane composition according to claim 2, wherein the (D) filler is at least one selected from the group consisting of aerosolous cerium oxide, precipitated cerium oxide, and calcium carbonate. The liquid-type room-hardening organopolyoxane composition of any one of the first to third aspects of the patent application, which further contains (E) a decane couple Mix 0.1 to 20 parts by mass.