JPH1077409A - Silicone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicone composition having good bondability to various adherends and having good rubbery elasticity, weathering resistance and durability by mixing a liquid polysiloxane polymer with a filler and microballoons in a suitable proportion. SOLUTION: This composition comprises 100 pts.wt. liquid polysiloxane polymer (A), 0.5-10 pts.wt. curing agent (B), 30-120 pts.wt. filler (C), 0.1-10 pts.wt. water and/or water dispersing agent (D) and 0.1-10 pts.wt. microballoons (E). It is desirable that the microballoons are hollow spheres having a mean particle diameter of 5.0-300μm and a true density of 0.1-0.9g/cc, that they are organic ones surface-treated with an inorganic substance and that they are made of an aluminosilicate. It has good adhesion to difficultly adhering coating materials such as fluorocarbon resin types and acrylic resin types, and a sealant containing this composition shows good bondability to various adherends when compared with a conventional sealant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone composition containing a liquid polysiloxane polymer and microballoons and having good rubber elasticity, weather resistance and durability.

[0002]

2. Description of the Related Art Conventionally, as a building sealant, a two-component silicone sealant having rubber elasticity, weather resistance, and durability is mainly used as a two-component silicone sealant, mainly composed of a liquid polysiloxane polymer and a filler. Two-component silicone sealants have been used. However, the sealing material having such a composition greatly affects the adhesiveness depending on the type of the filler to be blended. Usually, surface-treated precipitated calcium carbonate, heavy calcium carbonate, or the like is used as a filler for a building sealing material.

[0003]

However, a sealing material using such a filler depends on the type of the adherend to be adhered, and the suitability of the adhesion is affected, or a thixotropic material capable of withstanding use as a sealing material. This causes problems such as the inability to secure the performance. Therefore, a sealing material having stable adhesion to many adherends is desired. The present invention solves at least one of the above problems.

[0004]

In view of the present situation, the present inventors have made intensive studies to solve these problems of the conventional sealing material. The present inventors have found that a sealing material containing microballoons at an appropriate mixing ratio has good adhesiveness to various kinds of adherends, and have completed the present invention.

That is, the present invention relates to (A) 100 parts by weight of a liquid polysiloxane polymer, (B) 0.5 to 10 parts by weight of a curing agent, (C) 30 to 120 parts by weight of a filler, and (D) A silicone composition comprising 0.1 to 10 parts by weight of water and / or a water dispersant, and (E) 0.1 to 10 parts by weight of microballoons.

[0006] The average diameter of the microballoons is 5.0 to 5.0.
Preferably it is 300 μm. Micro balloon
It is preferably a hollow sphere having a true specific gravity of 0.1 to 0.9 g / cc. Preferably, the microballoon is a glass balloon. Preferably, the microballoon is a silica balloon. Preferably, the microballoon is a shirasu balloon. Preferably, the microballoon is an organic balloon. The microballoon is preferably an organic balloon surface-treated with an inorganic substance.
Preferably, the microballoon is an alumina silicate.

Hereinafter, the present invention will be described in more detail.
The liquid polysiloxane polymer used in the silicone composition of the present invention may be any polysiloxane polymer that is generally used for a two-part sealing material,
For example, dimethyl silicone, a diphenyl derivative of dimethyl silicone, a methylphenyl derivative of dimethyl silicone, a methyltrifluoropropyl derivative of dimethyl silicone, a tetrachlorophenyl derivative of dimethyl silicone, and the like can be given. In particular,

[0008]

Embedded image And the like. The viscosity of such a liquid polysiloxane polymer is 1,000 to 20,000 at 25 ° C.
It is preferably 0 cs.

The microballoons used in the silicone composition of the present invention include inorganic substances having a diameter of 1 μm to several hundred μm,
A hollow body made of a material such as an organic substance or a metal may be used, but a glass balloon, a silica balloon, a shirasu balloon, an organic balloon and the like are preferable. Glass balloon
It is a glass micro-hollow sphere having substantially no pores formed by foaming fine artificial glass. As the artificial silicon constituting the glass balloon, for example, an artificial glass such as a borosilicate glass, a borosilicate glass, or a silicate glass such as a silica balloon is used. The raw material for the Shirasu balloon is a volcanic eruption material such as pumice fall made of pumice tuff conglomerate, and its composition is usually SiO ₂ , Al ₂ O
₃ (alumina silicate), FeO, Fe ₂ O ₃ ,
It contains CaO, Na ₂ O, K ₂ O and the like. Examples of raw materials for the organic balloon include resins such as phenol, alkyd, amine, epoxy, polyester, polyamide, polyurethane, and polyvinylidene chloride. Further, an organic balloon surface-treated with an inorganic substance is preferable. Inorganic substances that can be used for the surface treatment include calcium carbonate, talc, titanium oxide, clay and the like.

Specifically, alumina silicate, acrylonitrile calcium carbonate (hollow body of acrylonitrile coated with calcium carbonate), acrylonitrile talc (hollow body of acrylonitrile coated with talc), borosilicate glass, borosilicate glass, silicon glass, etc. No. In addition, Philite manufactured by Philite, UK, and Microsphere 80GC manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
A, Microsphere 80GTA, Glass Bubbles S35 and S22 manufactured by Sumitomo 3M Co., Ltd. and bubble type C15 / 250, B23 / 500 of Glass Bubbles,
B28 / 750, B37 / 2000, B38 / 400
0, B46 / 4000, B60 / 10,000, E22 /
40. Floated series glass bubbles (bubble type A16 / 500, A20) manufactured by Sumitomo 3M Limited.
/ 1000, D32 / 4500) may be used.

The physical properties of the microballoon used for the silicone composition of the present invention are preferably from 5.0 to 300 μm, particularly preferably from 20 to 40 μm. The average particle size is
If it is less than 5.0 μm, the effect as a microballoon is reduced, and if it is more than 300 μm, the particle size is large and the appearance is rough.

The microballoon may have a hollow irregular shape, but a spherical shape is preferred from the viewpoint of kneading properties during production. The true specific gravity of the microballoon is 0.1-0.
It is preferably 9 g / cc, particularly preferably 0.3 to 0.7 g / cc. If it is less than 0.1 g / cc, there is a high possibility that the balloon will be broken during the production of the sealing material. In particular, when the micro balloon is a glass balloon, the average particle size of the glass balloon is 10 to 200 μm, and the average particle density is
0.1-0.6 g / cc, preferably 0.15-0.5
g / cc, bulk density is 0.05 to 0.5 g / cc, preferably 0.07 to 0.3 g / cc, and pressure resistance is 10 to 10 g / cc.
1000 kg / cm ² , preferably 15 to 300 kg /
Those having a cm ² and a bulk capacity of 90% or more are preferred.

The content of the microballoon in the silicone composition of the present invention is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 7 parts by weight, based on 100 parts by weight of the liquid polysiloxane polymer. The content of the micro balloon is
If it is less than 0.1 part by weight, there is almost no effect contained,
If the amount is more than 10 parts by weight, when the sealing material is applied to the surface of the adherend, the surface of the sealing material becomes uneven, which is not preferable.

As the curing agent used in the silicone composition of the present invention, a compound having an aminoxy group represented by the following formula (1) is preferable. Wherein R ¹ and R ² have 1 carbon atom
An alkyl group having from 5 to 5, preferably a methyl group or an ethyl group.

[0015]

Embedded image

Also, a bifunctional / trifunctional aminoxysiloxane manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

The content of the curing agent in the silicone composition of the present invention is preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight, based on 100 parts by weight of the liquid polysiloxane polymer. If it is less than 0.5 part by weight, curing will be poor,
If it exceeds 10 parts by weight, the physical properties are significantly different.

The filler used in the silicone composition of the present invention includes carbon black, clay, calcium carbonate, talc, magnesium carbonate, silica, titanium oxide and the like, and calcium carbonate, particularly surface-treated calcium carbonate, is preferred. The content of the filler in the silicone composition of the present invention is preferably 30 to 120 parts by weight, particularly preferably 40 to 100 parts by weight, based on 100 parts by weight of the liquid polysiloxane polymer. If the content of the filler is less than 30 parts by weight, the viscosity becomes too low, and if it is more than 120 parts by weight, the viscosity becomes too high and the workability is deteriorated.

The water and / or water dispersant (D) used in the silicone composition of the present invention includes water and a water dispersant. The content of water and / or water dispersant in the silicone composition of the present invention is determined by the liquid polysiloxane polymer 100
0.1 to 10 parts by weight, especially 0.1 to 10 parts by weight
It is preferably 0.5 parts by weight. The water includes water that inevitably enters the composition during storage or by reaction. The water dispersant is not particularly limited, but is preferably a polysiloxane-ethylene oxide copolymer. Particularly, a compound represented by the following formula (2) is preferable. R ^{3 to} R ⁵ may be the same or different and are hydrogen or a monovalent hydrocarbon group, and m, a, and b are integers of 1 or more.

[0020]

Embedded image

Also, L5340, L manufactured by Nippon Unicar Co., Ltd.
A commercially available product such as 5420 may be used. The content of the water dispersant is from 0.1 to 1.0 part by weight, especially from 0.1 to 0.5 part by weight, based on 100 parts by weight of the liquid polysiloxane polymer. It is preferred in that respect.

The silicone composition of the present invention may further contain, if necessary, a plasticizer, an antioxidant, a pigment and the like.

As a method for producing the silicone composition of the present invention, for example, component (A) a liquid polysiloxane polymer and (B) a curing agent are placed in separate containers, and component (C),
(D), (E), and if necessary, other additives are added to either (A) or (B), or both, and the mixture is stirred, placed in a container for storage, and mixed with the first liquid and the first liquid. Store as two solutions. At the time of use, the first liquid and the second liquid are mixed and used. In particular, the microballoon (E) may be added to only the first liquid to produce the first liquid, or may be added to the second liquid to produce the second liquid. Further, it may be manufactured by adding to both the first liquid and the second liquid. The silicone composition of the present invention is useful as a two-component silicone sealing material for buildings.

In the bonding method using the silicone composition of the present invention, if necessary, a primer composition is applied to an adherend, and then the silicone composition of the present invention is cast as a sealing material, The composition may be cured. Examples of the material of the adherend include a steel plate, an aluminum plate, anodized aluminum, and a resin plate coated with a hardly-adhesive resin such as a fluororesin or an acrylic resin. The adherends may be the same material for the two adherends or different materials. Furthermore, as the material of the adherend,
Adhering properly to glass etc.

As the primer composition used for adhesion,
Any primer may be used as long as it is a primer usually used for a silicone sealant. For example, a primer having the following composition 1 can be used. (Note: TPT: tetraisopropyl titanate)

In particular, when viewed from the combination of adherends,
When bonding a glass and a steel plate or an aluminum plate coated with a hard-to-adhesive paint such as a fluorine-based or acrylic resin, the silicone sealing material of the present invention has adhesiveness to various types of adherends. I have.

[0027]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited by these examples. (Examples 1 to 5 and Comparative Example 1) The component compositions shown in Table 1 below were kneaded at room temperature and in a vacuum atmosphere to obtain each of the silicone compositions of the present invention and the silicone composition of Comparative Example 1. Further, a primer composition having the following composition 1
X 50 mm in width, uniformly applied on two flat adherends (aluminum plate coated with fluorine or acrylic paint, heat reflection glass plate, anodized aluminum plate), JIS A
In accordance with 5758, a space formed by combining the two adherends and the spacer is filled with each of the produced silicone compositions, and the JIS A 5758 H-type (type 2) is used.
A test body was prepared. The adhesiveness was measured using the test piece, and the results shown in Table 1 were obtained.

The results of the adhesion test were determined according to the following criteria. (Primer composition 1) n-hexane 93 parts by weight Silicon resin (organopolysiloxane resin represented by the average unit formula of the following formula 3) 1.5 parts by weight Aminosilane 3.0 parts by weight TPT 2.5 parts by weight (Note: (TPT: tetraisopropyl titanate)

[0029]

Embedded image [Wherein, R ⁶ is a monovalent hydrocarbon group, R ⁷ is a hydrogen atom or an alkyl group, a is 0.8 to 1.8, and b is the number of hydroxyl groups or alkoxy groups bonded to silicon atoms in one molecule. Indicates a value that is monovalent or higher. ]

(1) Adhesiveness (a) Initial: The test piece was stored at 20 ° C. for 7 days, and further
After storage at 0 ° C. for 7 days, the adhesion was measured. (B) Water resistance: After the test pieces were initially stored, and further stored at 20 ° C. for 7 days, the adhesion was measured. The test was performed according to JIS A 5758.
The criteria for the determination are as follows. ：: CF: breaking of sealing material △: TCF: thin layer peeling ×: AF: interface peeling

[0031]

[Table 1]

Note: The amounts of each composition are given in parts by weight. Water dispersant: L5420 (manufactured by Nippon Unicar) Philite: alumina silicate (manufactured by UK Philite) Microsphere 80GCA: acrylonitrile / calcium carbonate (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) (average particle size: 15 μm, true specific gravity: 0. 23g / cc)

Microsphere 80GTA: Acrylonitrile talc (Matsumoto Yushi Seiyaku Co., Ltd.) (Average particle size: 15 μm, true specific gravity: 0.23 g / cc) S35: Borosilicate bubbles (Fuji Silysia Chemical Ltd.) (Average) Particle size: 34 μm, true specific gravity: 0.35 g / cc) S22: Glass bubbles (Sumitomo 3M) (average particle size: 25 μm, true specific gravity: 0.22 g / cc)

[0034]

Industrial Applicability The silicone composition of the present invention has good adhesiveness to hardly adherent paints such as fluorine-based and acrylic resins. Further, the sealant using the silicone composition of the present invention adheres to various kinds of adherends as compared with the conventional silicone sealant. The present invention has at least one of the above effects.

Continued on the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location C08K 9/02 C08K 9/02 C09J 183/04 JGG C09J 183/04 JGG

Claims (9)

[Claims] (A) 100 parts by weight of a liquid polysiloxane polymer, (B) 0.5 to 10 parts by weight of a curing agent, (C) 30 to 120 parts by weight of a filler, (D) water and / or A silicone composition comprising: 0.1 to 10 parts by weight of a water dispersant; and 0.1 to 10 parts by weight of (E) microballoons. 2. The microballoon having an average particle diameter of 5.
The silicone composition according to claim 1, which has a thickness of 0 to 300 µm. 3. The microballoon according to claim 1, wherein said microballoon has a hollow spherical shape and a true specific gravity of 0.1 to 0.9 g / cc.
3. The silicone composition according to item 1. 4. The silicone composition according to claim 1, wherein the microballoon is a glass balloon. 5. The silicone composition according to claim 1, wherein the micro balloon is a silica balloon. 6. The silicone composition according to claim 1, wherein the microballoon is a shirasu balloon. 7. The silicone composition according to claim 1, wherein the microballoon is an organic balloon. 8. The silicone composition according to claim 7, wherein the microballoon is an organic balloon surface-treated with an inorganic substance. 9. The silicone composition according to claim 1, wherein said microballoon is an alumina silicate.