JPS58101182A - Adhesive sealing material - Google Patents

Abstract

PURPOSE:An adhesive sealing material, containing a specific polydiorganopolysiloxane, a silicon compound containing aminoxy groups, a monohydric alcohol and an inorganic filler, and having improved adhesive property to general coating materials and spraying materials. CONSTITUTION:A sealing material containing (A) 100pts.wt. polydiorganosiloxane having terminal groups sealed by silanol groups and 100-200,000 cSt viscosity at 25 deg.C, (B) 0.1-30pts.wt. silicon compound containing aminoxy groups, having average more than 2 and less than 3 organoaminoxy groups linked to the silicon atom in the molecule, (C) 5-300pts.wt. inorganic filler, e.g. titanium oxide, and (D) 0.01-10pts.wt. monohydric alcohol, expressed by the formula ROH[R is a primary or secondary hydrocarbon group selected from the group consisting of monofunctional aliphatic hydrocarbon groups (except the group containing -C C-) and aralkyl groups], and having <0.1mm.Hg vapor pressure at 20 deg.C and <=20 deg.C freezing point.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesive sealants, and more particularly, to
Suitable as a sealant for the joints of built structures, it exhibits excellent adhesion (tackiness) at 1% without pre-treatment of the surface to be adhered to.
The present invention also relates to an adhesive sealant whose surface has good adhesion to general materials and spray materials.

A polyorganosiloxane composition that cures at room temperature to form a rubber-like elastic body has excellent heat resistance, cold resistance, and weather resistance.
There is little change in physical properties due to m.

It is widely used as a building sealant because it is less susceptible to deterioration due to ozone and ultraviolet rays. However, when adhering these curable polyorganosiloxane compositions to an adherend, pretreatment of the adhering surface is required (1), and adhesion may not be possible depending on the type of adherend. or,
External walls of buildings made of concrete, pre-cast concrete, lightweight concrete, or lightweight foamed concrete are coated with sealants such as T-YC, side walls, etc. for aesthetic reasons and for the purpose of providing watertightness to the exterior wall material itself. It is often painted over. Therefore, the sealant filled in the joints of these exterior wall materials! i! It is desirable to have a surface that can be coated with scissors, but curable silicone sealants have a certain point where the adhesion of general paint to the surface is poor and the paint film peels off. Ta.

Good l1lIllll without pre-processing the m-surface.
Examples of sealant compositions that can provide properties include:

A room temperature surface curable polyorganosiloxane composition disclosed in JP-A-56-86951 is mentioned. This composition consists of a diorganosiloxane end-capped with silanol groups, an aminoxy group-containing organosilicon compound having at least three aminoxy groups in each molecule directly bonded to a silane atom, a monohydric alcohol or an alkoxysilane, and an inorganic filler. It consists of According to this composition 1
Although the surface is hardened, the inside is sticky and semi-cured, resulting in a sticky elastic body, and this elastic body has good adhesion to adherends without any pretreatment. It means having a gender. however.

This elastic material has the problem that the hardened surface layer has adhesion with other general paints and spraying materials, which causes the applied A1 paint and spraying materials to peel off and fall off. In this respect, it is no different from conventional polyorganosiloxane sealants. However, according to the inventor's study, when used as a monohydric alcohol additive,
It has been found that when the Ml (@pressure is less than 0.1 μm at 20°C, the hardening of the surface layer of the elastic body does not proceed, and even after the inside has hardened, the surface layer remains sticky). It was done.

The present inventor has previously developed a wrinkled polyurethane resin that is cured at N temperature by a reaction between a silanol group end-capped polydiorganosiloxane and an aminoxy group-containing organic compound having an average number of organoaminoxy groups exceeding two in the molecule. By adding a primary or secondary monounsaturated alcohol having an alkynyl group to an organosiloxane composition, the resulting rubber-like elastic body forms on the surface and is used as a filler material for general paints. It was found that the adhesion with t7f4 was excellent. However, in order to adhere such an elastic body to an adherend, as with general curable compositions for sealers, it is necessary to pre-treat the adherend surface. There is a problem that it may be impossible to bond depending on the type of adherend.

On the other hand, as a non-curing sealant, one is shown in which a silicon compound containing two amino groups or aminoxy groups is added and reacted with a silanol group-terminated-ridiorganosiloxane. (IP# Kaisho 55-
66983). However, such sealants
Because it uses a silicon compound containing a 2-enriched 7-functional group or an aminoxy group, the reaction rate is extremely slow, and therefore it takes room temperature to develop adhesiveness and fully exert its function as a sealant. It takes 4 to 7 days.

During this process, it tends to rub off, crack, and run down due to rain, and the appearance deteriorates as a result, making it unsuitable for use as a sealing material for buildings.

The present invention 8A was developed in such a situation, and its purpose is to quickly increase the viscosity during use, maintain the viscosity without completely curing both the surface layer and the interior when the reaction is completed, and maintain the viscosity. The sealant exhibits good adhesion to the adherend without pretreatment, and has good adhesion to general paints and spray materials applied to the surface layer. The material is to provide.

As a result of extensive research, the present inventors have found that the number of silanol group-terminated polydiorganosiloxane molecules is more than 2 on average and less than 3 on average in one molecule.

Nopolyol-nosiloxane composition 171c, which normally cures by reaction with an aminoxy group-containing organosilicon compound having an organoaminoxy group, has a vapor pressure of less than (J, lmHg) at 20°C. 2nd grade 1ill
It is believed that the above objectives can be achieved by using a composition to which alcohol is added.

The present invention has now been completed.

Namely, the adhesive sealant of the present invention is as follows.

(A) Is the terminal end-capped with a silanol group and the viscosity at 25°C is 100 to 200,000 cst? 2100 parts by weight of lysoorganosiloxa.

(B) 0.1 to 30 parts by weight of an aminoxy group-containing silicon compound having an average number of more than 2 and less than 3 organoaminoxy groups bonded to silicon atoms in the molecule.

(C) 5 to 300 parts by weight of an inorganic filler, and 1 part by weight.

CD) The following general formula;
= represents a primary or secondary hydrocarbon group selected from the group consisting of (excluding those containing a c- group) and an aralkyl group. ), has a vapor pressure of less than 0.1 s+Hg at 20°C, and contains 0.01 to 10 parts by weight of a monohydric alcohol whose freezing point is below 20°C [Characteristics] It is.

In the following, the invention will be explained in more detail.

The polydiorganosiloxane of component (A) used in the present invention is a silanol-terminated I-ridiorganosiloxane which is usually used for condensed rmzv film assembly and is cured by filtering. The fineness at 25°C is 100 to 200,000 cS in order to give the material jI workability and physical properties suitable for use as a building sealant.
It is necessary that it be within the range of t. Viscosity is 100 as
If it is less than t, the adhesiveness will not be sufficiently developed after the reaction is completed.

If it exceeds 200.000 cst t-, a uniform composition will not be obtained and extrusion workability will deteriorate. A particularly preferable precision range is the sum of these two properties.

500 to 50,000 cst.

Examples of organic groups that are directly bonded to atoms in silicon 3 of polydiorganosiloxane include alkyl groups such as methyl, ethyl, globyl, butyl, and hexyl; alkenyl groups such as vinyl and allyl groups; phenyl groups; , aryl groups such as tolyl group; aralkyl groups such as pentyl group and phenylethyl group; 3゜3.3-)lifluoroglovir group, chloromethyl group, β-cyanoethyl group
Examples include Kanmin 1 Hizuyuki. Among these, methyl, vinyl, or phenyl groups are preferred due to ease of synthesis.
In particular, methyl groups are preferable because they are the most easily obtained raw material intermediates, provide the highest viscosity compared to polysiloxane 01, and are suitable for extrusion of sealants. In order to improve the balance between workability and physical properties, it is preferable that 85% or more of all organic groups be methyl groups, and it is more preferable that substantially all organic groups be methyl groups. However, if cold resistance or heat resistance is required, it is preferable to use a phenyl group as a part of the lr group.

The aminoxy group-containing 1-1-1-1-1-1 silicon-1 element compound of the component CB used in the present invention undergoes a dehydroxylamine reaction with the terminal silanol group of the polydiorganosiloxane of the component (A), thereby crosslinking and crosslinking the polysiloxane. It is for chain length extension, silane conductor and/or chain,
*- or branched 70xane derivatives may be used. The number of aminoxy groups contained in component (B) is determined to quickly increase the viscosity after use and reduce its function as a sealant.

It is necessary to have more than 2 on average in the molecule, and for the purpose of ensuring a sufficient pot life, on average 3
The number must be less than 1.

In order to obtain a sealing material having particularly good reactivity and excellent adhesiveness, it is preferable to use a combination of cyclic polysiloxanes containing two or three aminoxy groups in one molecule. Examples of organic groups to be bonded to the aminoxy group include methyl group, ethyl group, globyl group,
2 monovalent hydrocarbon water-collecting groups such as butylene group or cyclohexyl group, or 1 divalent swelling hydrogen group such as butylene group or pentylene group
Examples are given below. Among these, it is preferable to use an ethyl group because of the ease of obtaining raw materials, the reactivity of the injection field, and the ease of volatilization of the organohydroxylamine to be released. Examples of such aminoxy group-containing organosilicon compounds include the following. Hereinafter, for the sake of simplicity, the following abbreviations will be used for each V-machine silica compound.

(abbreviation) Me: methyl group, Et: ethyl group, nu-nibutyl group.

■i: Mini vinyl ph: Phenyl group EtzNQMe
mSiO8iMelONEk, Et*NQMesS
iOPh*SiO8iMhONEtS108i[OMe
lSiGJEtm)m # PhSi (OMemSi
The amount of such aminoxy group-containing organic compound added is selected from the range of 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of component (A). # of organosilicon compounds containing aminoxy groups
If the amount of fS7Jo is less than 0.1 part by weight, the reaction rate with the 72-nol-terminated polynoorganosiloxane will be too fast and sufficient working time will not be obtained, and if the amount added exceeds 30 parts by weight, the reaction will be delayed. The speed becomes slower, and after being used as a sealant, it takes a longer time to develop tack and function as a sealant, and during that time, it is more likely to rub off or crack.

The inorganic filler, component (C), used in the present invention imparts appropriate viscosity to the sealant and has the physical properties required for architectural sealants, depending on the purpose of use and processing conditions of the sealant. It is for satisfaction,
There is no particular limitation as long as it is an inorganic fine powder. As such an inorganic filler.

For example, fumed silica, precipitated silica, silica aerogel, ground silica, quince earth, iron chloride% titanium oxide, calcium carbonate, etc. are used. Ru.

The amount of such inorganic filler added is 100% of component (A).
5 to 3001 parts by weight, preferably 30 to 2 parts by weight
f#, 00 parts by weight. If the amount of inorganic filler is less than 5 parts by weight, the non-flowability necessary for use as a construction 7-ring material will not be obtained;
If it is too long, the workability will be low.

Such an inorganic filler may further include one colorant, for example,
Titanium oxide, acid nacopalt, #color iron oxide.

Cargan black, 1 phthalonanine pigment
An appropriate amount may be added in an amount normally used as a coloring material.

The monohydric alcohol used as component (D) in the present invention is used to maintain the adhesiveness of the sealant without completely curing the surface layer and inside thereof even when the reaction of the sealant composition is completed. . As a result, the sealant exhibits good layering properties on the adherend without pre-treatment, and also has good adhesion with general materials and spray materials applied to the surface layer. It is possible to trigger the

As mentioned above, such monohydric alcohols have % primary or secondary hydrocarbon groups and have a vapor pressure of 0.0% at 20°C.
It is selected from monohydric alcohols having a molecular weight of less than 1.

When the hydrocarbon group is tertiary, it is not preferable because it has a poor ability to maintain the adhesiveness of the surface layer and inside of the 7-ring material. In addition, if the vapor pressure at 20°C is 1 mm or more, the alcohol on the surface layer of the sealant will easily volatilize into the atmosphere, and the adhesiveness of the surface layer will disappear.
Good adhesion with general paints and spray materials cannot be obtained.

Furthermore, the CD) component has a freezing point of 20°C or lower, so it is necessary now! When the sealing material of the present invention is used in a relatively low temperature environment, the freezing point is preferably 10°C or lower, more preferably 0°C or lower. The reason for this is that when component (D) is in a solid state,
This is because the function of component (D) is not fully exhibited and the objective of the present invention cannot be achieved. (tX, ?lJ, t as a monohydric alcohol that can be used as a D component
Examples include n-decyl alcohol, undecyl alcohol, trimethylnonyl alcohol, noethertosodecyl alcohol, instearyl alcohol, oleyl alcohol, lylyl alcohol, etc., and one or more types selected from the group consisting of these. are used.

The amount of monohydric alcohol added is % (A) component 1
00 parts by weight, U, Ol -10 parts by weight, preferably in the range of 0.05 to 5 parts by weight. If the amount of monohydric alcohol is less than 0.01 parts by weight, the adhesiveness inside the sealant and on the surface cannot be maintained sufficiently, and the adhesion to the adherend and the adhesion of general hammers and spray materials will decrease. , while lO parts by weight? If it exceeds this, the crosslinking and thickening reaction will not proceed sufficiently and the function as a sealing material will deteriorate.Furthermore, not only will it not be possible to obtain the attachment force to the adherend, but also the adhesion of general materials and spray materials will be reduced.

The adhesive sealant of the present invention contains, among the above-mentioned components,
Usually, component (B) is a two-component type that is stored in a single container while the other components are mixed together and stored in the same state.
It is manufactured by a manufacturer.

The adhesive sealant of the present invention thus obtained is in the form of a paste that is easy to work with before and during use, and after the two liquids have warmed up, the workable time is sufficiently long at 1.5 to 3 hours. In addition, since the reaction progresses quickly after the work is completed, and the time required for the sealant to function as a sealant is within 12 hours, various problems may occur during curing. This is extremely rare. Furthermore, the adhesive sealant of the present invention has good adhesion to the adherend without pre-treating the surface of the adherend, and the sealant has excellent adhesion properties. It also has good adhesion to the sealant of the general paint and spray material applied to one surface. Therefore, the adhesive sealant of the present invention can be used not only as a sealant but also as a general paint or spray material. ! : #1 Suitable as a sealing material for buildings that require sealing.

In the following, the invention will be explained in more detail in Example II. In the examples, 1 part represents the weight S.

Example 1 A silanol end-capped polydimethylsiloxane Zoo@ having a viscosity of 5000 cst at 25°C was mixed with 50 parts of ground calcium carbonate having a % average particle i of 11 μm and an average particle size of 0.
25 parts of light calcium carbonate treated with 2s of stearic acid were added, and the mixture was kneaded once to obtain a base comparand.

(2) For 100 parts of pace compound, 6 weight -
3.0s of a crosslinking agent mixture consisting of
O~13 was obtained. At the same time, as a comparative example, a sample of Sal type was prepared. Sample 14 contains no monohydric alcohol, Sample 15 contains monohydric alcohol with a vapor pressure of 0.1 μm or more at 20°C, and Sample 16 contains monohydric alcohol whose freezing point exceeds 20°C. It is something. Among these, the stearyl alcohol of trial R16, the base con i'? The mixture was added to the powder, heated to 60° C., mixed, cooled to room temperature, and then prepared.

Next, a test # as shown in the drawing was prepared using the above samples 10 to 16. Such a test specimen.

Between two mortar plates with a length of 50 m and a thickness of 15 mm,
The sample was filled to a length of 15 cm.

The test specimen thus prepared was aged and hardened at room temperature for 14 days, and then subjected to a tensile test. The results are shown in Table 2.

In addition, samples 10 to 16 were coated on a slate board to a thickness of 15 coats, and cured at room temperature for 14 days to form a second layer on the sample surface.
'f! Apply each of the paints shown in l to the skin.

After applying the paint, it was dried for 7 days at room temperature, and then the surface of the paint was coated with 11i20■ Gas 2 Cross Stag T-, cyanoacrylate adhesive (Toagosei Kagaku Co., Ltd. #!, Allo/Alpha, trade name). Glued. After sufficient adhesion, measure the peeling stress between the paint film and the sample by pulling one end of the glass cloth tape.

The results are also shown in Table 2.

Example 2 00 parts of silanol end-capped I lydimethylsiloxane having a viscosity of 3000 cst at 25°C.

Rosin acid-treated colloidal calcium carbonate 6 with an average particle size of 0.6μ
5 parts were added and t-mixed to obtain a pace compound.

5111% for 100 copies of this pacecon/4 round
3.5 parts of a crosslinking agent mixture consisting of: and a monohydric alcohol in the amounts shown in Table 3 were added and mixed.

20-25t of IK was obtained. At the same time, as a comparative example, a sample without the addition of monohydric alcohol (sample 26) was prepared.

Using these samples, pull! in the same manner as Example 1.
I test and peel stress measurements were conducted. 31st in the result!
shown at the same time.

Example 3 100 parts of silanol-terminated polyzomethylsiloxane having a viscosity of 12,000 cSt at 25°C was added with an average particle size of 100 parts. ! Light calcium carbonate 50!5 of 0.5μ and stearic acid-treated calcium colloid acid 2 of average particle size 0o05μ
5 parts were added and mixed to obtain a pace compound.

(For 100 parts of Nopace Compact,
Samples 30 and 31 were prepared by adding 2.5 parts of a crosslinking agent mixture consisting of
'i got it. As a comparative example, a sample to which no monohydric alcohol was added (sample 32) was prepared.

Using these samples, the test specimens shown on the foam surface were prepared, and after curing and hardening at room temperature for 14 days, the! The paints and spray materials shown in Table 4 were applied to the I2 side. Next, after curing and curing at room temperature for 7 days, the test specimen was mounted on a fatigue testing machine, and a displacement of ±10− with respect to the sample joint width was repeatedly applied 2000 times. Visually observed. The results are also shown in Table 4.

Example 4 Same samples 11, 12 and 1 as used in Example 1
An extrudability test according to JIS A3758 was conducted using 3T, and the number of seconds for extrusion was measured 1.5 hours after mixing the sample. The results are shown in Table 5. In addition, according to JIS A3758, the time when the number of extrusion seconds reaches 20 seconds is defined as the pot life.

As is clear from the results shown in Table 5, the adhesive sealing material of the present invention exhibits good adhesion to the adherend (kJt) without pretreatment; and,
General I applied to the surface layer! ! The adhesive sealant of the present invention can also be used as a spray material.

It is sure that the adhesive has good adhesion and does not break.

[Brief explanation of drawings]

FIG. 1C is a perspective view of a tensile test specimen. l...sample, 2...mortar material. Procedural Amendment May 26, 1980 Director General of the Patent Office Shima 1) Haruki Tono], Incident Indication USE 'FLP Permit A No. 200111 No. 2
・Name of the invention Adhesive sealant material 3. Relationship with the person making the amendment Name of patent applicant: Toshiba Silicone Co., Ltd. (Name) 5. Date of amendment order Voluntary action 6. Number of inventions increased by the amendment None 7, Subject of amendment Detailed explanation of the invention in the specification O column 8, Contents of amendment The column of the detailed explanation of the invention in the specification is amended as follows. (1) Page 7, line 1 of the specification, K "silicon compound J" is corrected to "silicon compound only." 0) Correct it to the 3rd line from the 12th line of the detailed statement.

Claims (1)

[Claims] 1. (A) The terminal is blocked with a silanol group, 25°C,
The viscosity ranges from 100 to 200,0OOC8t "C"
100 parts by weight of a certain polydiorganosiloxane. (B) Aminoxy group-containing silicon compound having more than 2 but less than 3 silicon-bonded organoaonoxy groups in the molecule, 0 = 1 to 30 parts by weight, (C ) 5 to 300 parts by weight of an inorganic filler. as well as. (D) The following general formula: (In the formula, selected from the group consisting of R, a monovalent aliphatic hydrocarbon group (excluding those containing a -C-C- group), and an aralkyl group. ) containing 0.01 to 10 parts by weight of a monohydric alcohol having a vapor pressure of less than 0.1 ■Hg at 20°C and a freezing point of 20°C or less, and is defined as t% mold. Adhesive sealant. 2. The freezing point of component (D) monohydric alcohol is 10℃
An adhesive sealing material according to claim 1 below. The adhesive sealing material according to claim W42, wherein the monohydric alcohol as the component (D) has a freezing point of 0° C. or lower. 4 The organic group bonded to the silicon atom of component (A) is 85
Patent claim 0flA, which is 1s or more metek group, 1st! J
The adhesive sea cinder material described in I. 5. The adhesive sealing material according to claim 18II, item 41, wherein the organic group bonded to the 7-minoxy group of component (B) is an ethyl group. The adhesive sealing material according to claim 1, wherein the amount is 1 to 15 parts by weight based on sK. 7. Claim 1, wherein the amount of component (C) added is 30 to 2001 parts per 100 parts by weight of component (A).
Adhesive sealant as described in section. 8. Claim 1, wherein the amount of component (L) added is 05 to 5 parts by weight per 100 parts by weight of component (A).
Adhesive sealant as described in section.