JPS62124149A - Curable composition - Google Patents

Abstract

PURPOSE:A room temperature curable composition providing a film of coating having improved solvent resistance, impact resistance, etc., comprising an alkenoxy group-containing organopolysiloxane and an alkoxysilane (partial hydrolyzate) and an organotin compound. CONSTITUTION:(A) 100pts.wt. alkenoxy group-containing organo-polysiloxane shown by formula I (R' is 1-18C monofunctional hydrocarbon group; R<2> and R<3> are H or 1-8C monofunctional hydrocarbon group; 0.8<=n<=1.8; 0<m<2) obtained by silylating a hydroxyl group of a silanol group-containing organopolysiloxane with an alkenoxysilane compound is blended with (B) 0.01-20pts.wt. alkoxysilane (partial hydrolyzate) shown by the formula II or formula III (R<4> and R<5> and H, alkyl, etc.; R<6> is 1-6C bifunctional hydrocarbon group; R<7> and R<8> are 1-8C monofunctional hydrocarbon group; q is 0 or 1) and (C) 0-10pts.wt. organotin compound (dibutyltin diacetate, etc.,).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a crushable composition, a special metal, a plastic,
Room-temperature silicone containing algenoxy group-containing organopolysilochitin as a main ingredient, which is used to protect the surfaces of various objects such as ceramics, glass, and wood, to provide stain resistance, electrical insulation, and powder fluidity. The present invention relates to a chemical composition.

(Prior art) The purpose of imparting impact resistance, solvent resistance, mold releasability, water repellency, weather resistance, heat resistance, electrical insulation, etc. to the surfaces of various objects such as metals, plastics, ceramics, glass, and wood. Coating with a silicone resin composition 55C has already been widely practiced, and organopolysilochitin resin having a hydroxyl group bonded to a silicon atom is widely used as the silicone resin composition.

Curing of this type of organopolysilochitin resin has conventionally been carried out by heating the film to a high temperature of 150°C or higher, but a room-temperature-curable silicone resin containing an alkyl acetoxysilane is used. (see U.S. Pat. No. 2,615,861), and room-temperature-curable silicone resin compositions containing aminoalkyl alkoxysilanes (see U.S. Pat. No. 3,350,34).
9) are also known. However, these resin compositions have very poor storage stability and must be mixed immediately before use, and the cured film has the disadvantages of poor solvent resistance and poor adhesion.

Therefore, in order to improve the storage stability of this type of composition, a composition comprising a ketoxime group-containing organopolysiloxitin and an aminoalkylalkoxysilane has been proposed (see Japanese Patent Publication No. 1971-1fi547). This C has the disadvantage that the ketoxime generated during curing is toxic and corrosive, so it cannot be used for copper coating. Room-temperature curable compositions containing alkoxysilanes (see Japanese Patent Publication No. 15827/1982) have good storage stability and are not corrosive, but it takes a long time for the film to form internally, and The odor has a disadvantage of being inferior in strength (2).Also, this composition (2) is known to be crosslinked with a diorganoborisilane organosilane in which both ends of the molecular chain are blocked with hydroxyl groups (Japanese Patent Publication Show F11- No. 39274, Special Publication No. 51-396
73, Japanese Patent Publication No. 54-44699), but these compositions are soft and difficult to form into thin films, and are used as protective coatings for various substrates to impart impact resistance, solvent resistance, etc. The disadvantage is that it cannot be done.

(Structure of the Invention) The present invention relates to a room-temperature curable coating agent composition that solves these disadvantages, in which R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms. ,R,
R is each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n%m is each 0.8≦n≦
1.8.0<m<2J Alkenoquine group-containing organopolysilochitin 100 parts, 2) General formula R, R
is an atom or group selected from hydrogen atom, alkyl group, aryl group, aminoalkyl group, N-alkylaminoalkyl group, N, N-dialkylaminoalkyl group, alkylene group, okynealkylene group, R6 has 1 carbon number ~6 unsubstituted or substituted divalent hydrocarbon groups, R' and R8 are each unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms,
q is 0 or 1) 0.01 to 2 parts of an alkoxysilane or a partially hydrolyzed product thereof, and 3) O to 10 parts of an organic atom compound.

That is, as a result of various studies by the present inventors on room temperature curable compositions that do not have the disadvantages and drawbacks described above,
In the case where the alkenoxy group-containing organopolysiloxane represented by the above general formula is used as the main ingredient and an alkoxysilane represented by the above general formula or its partial hydrolyzate is added, all the hydroxyl groups involved in the crosslinking C2 are alkenoxy groups. Because it is capped with silyl groups, it does not condense in the absence of moisture and can be stored stably for at least 6 months, and during curing, active silanol groups are released as ketones are eliminated. It was discovered that because the film is instantly condensed and crosslinked, the resulting film has high adhesion, and has excellent impact resistance, bending resistance, and solvent resistance. completed the present invention by confirming that only harmless ketones are released during curing, and no toxic or corrosive gases such as amines, acetic acid, ketoxime, etc., which have been problems in the past, are emitted.

No. 1531 constituting the curable composition of the present invention: represents an organopolysiloxane containing an alkenoxy group, R is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a dodecyl group, an octadecyl group, etc. Alkyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and tolyl groups, or some or all of the hydrogen atoms bonded to the carbon atoms of these groups. 1 carbon number selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc., substituted with halogen atom, cyano group, etc.
~18 unsubstituted or t is a substituted monovalent hydrocarbon group, R and R are hydrogen atoms or unsubstituted or substituted monovalent hydrocarbons having 1 to 8 carbon atoms similar to R1, n and m are each 0.8≦ n≦1.
8, O < m < 2, but this m value is 0 from the viewpoint of the strength of the film obtained from this composition.
．． 01 < m < 0.5, and examples thereof include the following.

10H2 ((Oust (8i0) 10(3HI 3
p1.11 1.4 \cH3o,og
a (PI'='6 is a positive number of 3 or more]
This alkenoxy group-containing organosilochitin is a silanol group-containing organopolysilochitin (R", R
", R" are the same as above, r is O or IJ, and it can be obtained by silylation with an alkenoxysilane compound or a partial hydrolyzate thereof. Therefore, in this production, O28 to 1 per silicon atom
．． One or a mixture of two or more chlorosilanes having eight monovalent hydrocarbons is hydrolyzed in the presence of an organic solvent to produce silanol group-containing organosilochitin, which is optionally polymerized to form silanol groups. By reacting an organosiloxane obtained by condensing a part of with an alkenoxysilane or a partial hydrolyzate thereof, the hydroxyl group is silylated at room temperature to produce an alkenoxy group-containing organopolysiloxane represented by the above formula (1). can be obtained. However, if this organosilochitin contains less than 0.01% by weight of alkenoxy groups bonded to silicon atoms, crosslinking will not proceed effectively even in the presence of aminoalkylalkoxysilane, which will be described later, and a cured film will not be formed. If this value is exceeded, there will be too many functional groups and the film will become brittle.
It is necessary to set the value of m so that it is in the range of 0.001 to 40% by weight. For this reason, the degree of polymerization must be adjusted so that the content of crudely bonded hydroxyl groups in the silicon atom I of the raw material resin falls within this range, but as an alkenoxysilane compound that can be silylated is methyltri(impropenyl oxy V) silane, vinyltri(
isopropenyloxy) 17rane, phenyltri(infurobenyloxy)silane, propyltri(isopropenyloxy)silane, tetra(isopropenyloxy) V
Silane, methyltri(1-phenylethynyloxy)silane, methyltri(1-isobutenyloxy)silane,
Examples include methyltri(1-methyl-1-propenyloxyfusilane) and partial hydrolysates thereof.

Next, the aminoalkylalkoxysilane as the second component constituting this curable composition is represented by the general formula (%), where R4 and R8 are hydrogen atoms, alkyl groups, aryl groups, aminoalkyl groups, N- An atom or group selected from alkylaminoalkyl M, N, N-dialkylaminoalkyl group, alkylene group, oxyalkylene group,
R is an unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms such as a methylene group, ethylene group, propylene group, or phenylene group;
R is the same unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms as R1, and q is 0 or 1. When it acts as a fecalization promoter, it also improves the adhesion of the abrasive film obtained from the composition of the present invention to the substrate, and further reduces the amount of charge on the object coated with this composition. It can be controlled. These compounds include 3-aminopropyltriethoxysilane, 3-(N,N-dimethylamino]propyltriethoxyvvlan, 3-(2-7minoethylamino)propyltrimethoxysilane, and 3-morpholinopropyltriethoxysilane. Ethoxysilane, 3-aminopropylmethyljethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(N-methylamino]propyltriethoxysilane, 3-piveridinopropyltriethoxysilane , 3-(N, N, N, N-tetramethylguanidinopropyl)trimethoxysilane, 3-(N
, N, N, N-tetramethylguanidinoprobyl J methyldimethoxysilane, 3-(N,N-ethylmethyl-N.

N'-ethylmethylguanidinopropyl)trimethoxysilane, 3-(N,N-/tylphenyl-N.

N'-methylphenylguanidinopropyl)trimethoxysilane, 3-(N, N, N', N'
Examples include -tetramethylguanidinopropyl)tri(isopropenyloxy)silane and partial hydrolysates thereof. If the amount of this second loss is less than 0.01 part by weight based on 100 parts by weight of the alkenoxy group-containing organopolysiloxane as the first component, the curability of this composition will be poor and the resulting cured film will be poor. The adhesion to the base material will also be poor, and if the amount exceeds 20 parts by weight, the resulting cured film will undergo significant discoloration at high temperatures.
A range of 01 to 20 military units is required.

In addition, in order to accelerate the reaction of the composition of the present invention, an organic tin compound is added as a third component if necessary, but this is usually used in the dehydration condensation of silanol. Examples include acetate, dibutyl diacetate, dibutyl dilaurate, octylic acid diacetate, naphthenic acid diacetate, etc.
It may be added within the range of q parts by weight.

The curable composition 5y of the present invention can be obtained by uniformly mixing predetermined amounts of the above-mentioned first to third components. If the first component has a relatively high viscosity, it is recommended to dilute it with an organic solvent for coating purposes. Examples include gasoline, cyclohexane, trichloroethylene, 1.1.1-trichloroethyne, chloroform, and carbon tetrachloride, but toluene, which has a high solubility of organopolyi/loxane,
Preferably, it is xylene.

As mentioned above, the coating composition of the present invention obtained as described above can be stored stably for at least 6 months, and upon curing, it releases ketones and rapidly becomes thick, and the resulting aging film is coated with Metals,
Silicone films with excellent physical properties can be formed on the surfaces of plastics, ceramics, glass, wood, etc., but the faecal films obtained by C2 are hard, and have good bending resistance, impact resistance, and solvent resistance. It is a coating that protects processed objects from the effects of light, air, water, corrosive gases, solvents, etc., as it has excellent properties such as water repellency, mold releasability, water repellency, weather resistance, heat resistance, and electrical insulation. Coating agents to prevent the adhesion of powder, dirt, dirt, water scale, etc. - Coating agents to make the surfaces of various objects electrically insulating, coatings to reduce resistance when flowing various powders It is said to be useful as a medicine. Note that this coating composition can be applied to various base materials such as those mentioned above, so specifically, it can be applied to transportation equipment such as automobiles and various vehicles;
Useful for electrical and electronic equipment such as relays, terminals, printed circuit boards, electrical contacts, construction applications such as pipes, bridges, buildings, tiles, window glass, etc., and for processing various molds, utility poles, cooking utensils, ferrite powder, iron powder, etc. It is said that

Next, examples of the present invention will be given, in which the parts in the examples indicate heavy sliding parts, and the various test results in the examples are the results obtained by the following method C.

(Pencil lll1! degree)...JIS K5400.6
- According to paragraph 14.

(Adhesion)...JIS K5400.6-15
〇 (Flexing resistance)...according to JIS K5400.6-16 (mandrel) Test 2ff171φ).[○...
Pass, ×...Fail] (Impact resistance)... fduPont type 1/2 inch x 500g according to JIS K5400.6-13
50 CrfL l. [○...Pass, ×...Fail] (Solvent resistance)...100g of gauze soaked in xylene
It is expressed as the number of reciprocations until the film peels off when the film is reciprocated under a load of .

(Heat resistance) Changes in the appearance of the film after heating at 250° C. for 24 hours were observed with the naked eye.

[O...no abnormality, ×...abnormality] (accelerated weather resistance)...Atlas Cobucon (ultraviolet irradiation 70°CX8
After 2,500 hours of a 4-hour cycle of 50° C. and humidity, the external appearance of the film was visually observed.

[○: No abnormality;

(Corrosion)...Coating agent 5QX150
It was applied to a copper plate of XO, 38, and the surface condition was observed with the naked eye after being left at room temperature for one month.

Examples 1 to 5, Comparative Examples 1 to 2 80 mol% of methyltrichlorosilane (CH,5iOj3) and dimethyldichlorosilane ((cH,)2SiOj,
) and 20 mol% in the presence of toluene (two-coat water decomposition) to form silicon (0.8% by weight of dibonded hydroxyl groups, 1.2% by coul)
After making a 50% toluene solution A%B, C of 3M organopolysilochitin containing 1.5% by volume, the following alkenoxysilanes a and b were added to 100 parts of this organopolysilochitin. The amounts shown in Table 1 were used to react under nitrogen gas atmosphere at room temperature for 2 hours to produce the alkenoquine group-containing organopolysilochitins I to 1 shown in Table 1.

(Alkenoxysilane) - 100 parts of this alkenoxy group-containing organopolysilochitin (Table 2) - The indicated amounts of aminoalkyl alkoxysilanes c, d, e, f and an organic compound Coating compositions 1 to 5 are prepared by adding
0x150x0.3m polished mild steel plate ≦; thickness 20μrr
After pouring it into L and leaving it to harden at room temperature for 48 hours, I examined the physical properties of the resulting cured film C.'
fJ3 table (two and three results were obtained).

(Aminoalkylalkoxysilane) C-(OHsJ!N(OH,), 5i(00,H,),
(OH8O), 5i (OH, 0H20H,)8, e ・
・・HKN (0H2)s Si (002Hs)
3, f...((OH,), N320=N(OH
2+, SL (OCF (3) 3°) 1 For comparison, instead of the alkenoxy group-containing organosilochitin used above, 100 parts of 50% toluene solution B of the organopolysilochitin containing the hydroxyl group obtained above was used. Nimethyltrimethoxy ν run (C) (Si(○OH,), :11
5 parts or methyltris(ethylmethylketoxime)silane luganovorisiloxane V, Vl was prepared, and then 5 parts of the above-mentioned aminoalkylalkoxysilane d and 1 part of dibutyltin diacetate were added to this organopolysiloxane ■ and 3 parts of W2O. Make coating agent 6.7,
When these physical properties were examined, the results were shown in Table 3.

Procedural amendment: ll (flu 6014 December 24) 1, Indication of the case 1985 Patent A!264298 2, Name of the invention Curable composition 3, Person making the amendment Relationship to the case Name of the patent applicant (206) Shin-Etsu Chemical Co., Ltd. 4, Agent Address: Nagai Building, 4-9 Nihonbashi Honmachi, Chuo-ku, Tokyo 103 [Niss Tokyo (270) 0858.0859]
6.? [, N, N, N-tetramethyl] in line 1404 of the ``Detailed Description of the Invention'' section 1 of the specification of Heavy Industries
N, N, N', N'-tetramethyl".

2) ``NHOHOHNH (OH,O),5ifOH20H20H,'' on page 22, line 12 of the specification
H. , 38□. H2)3NHOH,. H7NH2J
,! [I do.

Below

Claims (1)

[Claims] 1, 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R^1 is unsubstituted or substituted 1 having 1 to 18 carbon atoms.
R^2 and R^3 are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n
, m is 100 parts by weight of an alkenoxy group-containing organopolysiloxane, each represented by 0.8≦n≦1.8, 0<m<2), 2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formula , chemical formulas, tables, etc. ▼ (Here, R^4 and R^5 are hydrogen atoms, alkyl groups, aryl groups, aminoalkyl groups, N-alkylaminoalkyl groups, N,N-dialkylaminoalkyl groups, respectively.
Atom or group selected from alkylene group and oxyalkylene group, R^6 is unsubstituted or substituted 2 having 1 to 6 carbon atoms
valence hydrocarbon group, R^7 and R^8 each have 1 to 8 carbon atoms
unsubstituted or substituted monovalent hydrocarbon group, q is 0 or 1)
A curable composition comprising: 0.01 to 20 parts by weight of an alkoxysilane or a partially hydrolyzed product thereof; and 3) 0 to 10 parts by weight of an organotin compound.